Nitro group terminated mesogenic epoxy resin adducts

ABSTRACT

Adducts containing terminating nitro (nitroso) groups and one or more mesogenic moieties are prepared by reacting (A) at least one compound containing an average of more than one vicinal epoxide group per molecule with (B) at least one compound containing one or more nitro (nitroso) groups and an average of one reactive hydrogen atom per molecule; with the proviso that at least one member of components (A) and (B) contains a mesogenic moiety. Reduction of these adducts provides amines which are useful as curing agents for epoxy resins.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of application Ser. No. 08/154,805 filedNov. 18, 1993 (now U.S. Pat. No. 5,394,898) which is a division ofapplication Ser. No. 07/982,804 filed Nov. 30, 1992 (now U.S. Pat. No.5,298,575) all of which are incorporated herein by reference in theirentirety.

FIELD OF THE INVENTION

The present invention concerns adducts of epoxy resins, which adductscontain terminating nitro (nitroso) groups as well as one or moremesogenic moieties.

BACKGROUND OF THE INVENTION

Application Ser. No. 07/562,289 filed Aug. 3, 1990 (now U.S. Pat. No.5,276,184) teaches the preparation of adducts of epoxy resins and activehydrogen containing compounds, one or both of which contain one or moremesogenic moieties, as well as thermosettable compositions containingone or more of said adducts and products resulting from curing curablecompositions thereof. In that invention, a plurality of active hydrogens(at least two or more) are required to be present in the active hydrogencontaining compounds used to prepare the epoxy resin adducts. Thus, theactive hydrogens of the active hydrogen containing compounds used in thepreparation of the adducts, react, in part, with the epoxy groups of anepoxy resin also used in the preparation of the adducts and remain, inpart, unreacted for future use as reactive moieties in a curablecomposition. When used to cure an epoxy resin, the mesogen-containingepoxy resin adducts of that invention provide cured products possessingsubstantial enhancement of physical and mechanical properties.

The present invention provides nitro (nitroso) group terminated adductsof epoxy resins prepared via reaction of an epoxy resin with a singleactive hydrogen containing compound which simultaneously contains one ormore nitro (nitroso) groups. The resultant adducts of the presentinvention thus contain nitro (nitroso) terminating groups with no activehydrogen contributed by the single active hydrogen containing compoundused to prepare said adduct. The advantages of the nitro terminatedmesogen-containing adducts of the represent invention are multiple: A.)Reduction of the nitro groups provides a primary amine terminated adductfree of the chain extension (advancement) and/or branching potentiallyencountered if an aminophenol and an epoxy resin are reacted directly inan attempt to obtain the primary amine terminated adduct. B.) Reductionof the nitro groups provides exclusive primary amine termination in theadduct, whereas some extent of phenolic hydroxyl termination is likelyif an aminophenol and an epoxy resin are reacted directly in an attemptto obtain the primary amine terminated adduct. Because of the higherreactivity of the amine group versus the phenolic hydroxyl group, thephenolic hydroxyl termination is, in fact favored under many conditionsof reaction. If chain extension (advancement) through the primary aminegroup occurs (i.e., reaction of the primary amine hydrogens with twoepoxide groups in separate epoxy resin molecules), a tertiary aminegroup becomes fixed in the adduct structure. C.) Functionalization ofthe backbone aliphatic hydroxyl groups, which result from epoxide ringopening by an active hydrogen containing compound to form an adduct, isvery difficult in the presence of active hydrogen groups remaining in anadduct for future use as reactive moieties in a curable composition. Byway of contrast, in the present invention, the nitro group terminatedadducts with no active hydrogen contributed by the single activehydrogen containing compound used to prepare said adduct, may befunctionalized through reaction of the backbone aliphatic hydroxylgroups without undesirable coreaction. The nitro groups present in thefunctionalized adduct are then reduced to provide primary aminetermination for future use as reactive moieties in a curablecomposition. These amine terminated, functionalized adducts arepreferred compositions of the present invention due to the liquidcrystallinity often induced as a result of functionalization of thebackbone aliphatic hydroxyl groups and improved processability resultingfrom lower melting temperatures.

SUMMARY OF THE INVENTION

The present invention concerns adducts containing terminating nitro(--NO₂) or nitroso (--NO), hereinafter designated as "nitro (nitroso)"groups and one or more mesogenic moieties which are prepared by reacting

(A) one or more epoxy resins containing one or more mesogenic moieties,one or more epoxy resins free of mesogenic moieties, or mixturesthereof, and

(B) at least one of (1) one or more single active hydrogen containingmaterials containing one or more nitro (nitroso) groups and one or moremesogenic moieties per molecule, (2) one or more single active hydrogencontaining materials containing one or more nitro (nitroso) groups freeof mesogenic moieties, or (3) a mixture of (1) and (2), with the provisothat one or more mesogenic moieties are present in either (A), the epoxyresin reactant or (B), the material containing one hydrogen which isreactive with an epoxide group or in both (A) and (B).

Another aspect of the present invention concerns adducts containingterminating nitro (nitroso) groups and one or more mesogenic moietieswhich have been partially or totally functionalized via reaction of apart or all of the backbone aliphatic hydroxyl groups.

Another aspect of the present invention concerns adducts containingterminating primary amine groups and one or more mesogenic moietieswhich have been partially or totally functionalized via reaction of apart or all of the backbone aliphatic hydroxyl groups.

Another aspect of the present invention concerns thermosettable(curable) mixtures of one or more of the aforesaid partially or totallyfunctionalized adducts with one or more epoxy resins.

Another aspect of the present invention concerns the product resultingfrom thermosetting (curing) one or more of the aforesaid thermosettable(curable) mixtures.

A further aspect of the present invention pertains to products resultingfrom orienting any of the aforesaid thermosettable (curable) mixtures.

The term "mesogenic" as is used herein designates compounds containingone or more rigid rod-like structural units which have been found tofavor the formation of liquid crystal phases in the case of low molarmass substances. Thus the mesogen or mesogenic moiety is that structureresponsible for molecular ordering. The term "mesogenic" is furtherdefined by R. A. Weiss (ed.) and C. K. Ober (ed.) in Liquid-CrystallinePolymers, ACS Symposium Series 435 (1989) on page 2: "The rigid unitresponsible for the liquid crystalline behavior is referred to as themesogen," and "Liquid crystalline order is a consequence solely ofmolecular shape anisotropy, such as found in rigid rod-shaped molecules. . . " Further definition of the term "mesogenic" may be found inPolymeric Liquid Crystals, Alexandre Blumstein (ed.), (1983) on pages2-3 and in Polymeric Liquid Crystals, A. Ciferri, W. R. Krigbaum andRobert B. Meyer (eds.) (1982) on pages 5-9, both of which areincorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION Epoxy Resin Component

Suitable epoxy resins which can be employed herein include essentiallyany epoxy-containing compound which contains an average of more than onevicinal epoxide group per molecule. The epoxide groups can be attachedto any oxygen, sulfur or nitrogen atom or the single bonded oxygen atomattached to the carbon atom of a --CO--O-- group in which said oxygen,sulfur or nitrogen atom or the carbon atom of the --CO--O-- group isattached to an aliphatic, aromatic or cycloaliphatic hydrocarbon groupwhich hydrocarbon group can be substituted with any inert substituentincluding, but not limited to, halogen atoms, preferably chlorine orbromine, nitro groups and the like or the oxygen, sulfur, nitrogen atom,or the single bonded oxygen atom attached to the carbon atom of a--CO--O-- group can be attached to the terminal carbon atom of acompound containing an average of more than one --(--CHR^(a)--CHR^(a))_(t) -- group where each R^(a) is independently hydrogen or analkyl or haloalkyl group, containing from 1 to about 2 carbon atoms,with the proviso that only one R^(a) group can be a haloalkyl group, andt has a value from 1 to about 100, preferably from 1 to about 20, morepreferably from 1 to about 10, most preferably from 1 to about 5.

It should be understood that in those instances wherein it is requiredthat the epoxy resin or epoxy-containing compound contain a mesogenicmoiety that those epoxy resins or epoxy-containing compounds which donot contain a mesogenic moiety are not suitable for that particularpurpose.

Particularly suitable epoxy resins which can be employed herein includethose compounds having an average of more than one vicinal epoxide groupper molecule, such as, for example, the glycidyl ethers or glycidylamines represented by the following formulas ##STR1## wherein each A isindependently a direct single bond, a divalent hydrocarbyl group havingfrom 1 to about 20, preferably from 1 to about 14, carbon atoms, --O--,--CO--, --SO--, --SO₂ --, --S--, --S--S--, --CR¹ =CR¹, --C.tbd.C--,--N═N--, --CR¹ ═N--, --O--CO--, --NR¹ --CO--, --CR¹ ═N--N═CR¹ --, --CR¹═CR¹ --CO--, --N═CR¹ --, --CO--O--, --CO--NR¹ --, --CO--CR¹ ═CR¹ --,--CO--O--N═CR¹ --, --CR¹ ═N--O--OC--, --CO--NR¹ --NR¹ --OC--, --CR¹ ═CR¹--O--OC--, --CO--O--CR¹ ═CR¹ --, --O--OC--CR¹ ═CR¹ --, --CR¹ ═CR¹--CO--O--, -- (CHR¹)_(n') --O--CO--CR¹ ═CR¹ --, --CR¹ ═CR¹--CO--O--(CHR¹)_(n') --, --(CHR¹)_(n') --CO--O--CR¹ ═CR¹ --, --CR¹ ═CR¹--O--CO--(CHR¹)_(n') --, --CO--S--, --S--OC--, --CH₂ --CH₂ --CO--O--,--O--OC--CH₂ --CH₂ --, --C.tbd.C--C.tbd.C--, --CR¹ ═CR¹ --CR¹ ═CR¹ --,##STR2## A' is a divalent hydrocarbyl group having from 1 to about 10,preferably from 1 to about 4, carbon atoms and in Formula IV, A' canalso contain one or more heteroatoms selected from N, O, S, and the likeand may be saturated or unsaturated; each A¹ is independently a ##STR3##each R is independently hydrogen or a hydrocarbyl or hydrocarbyloxygroup having from 1 to about 10, preferably 1 to about 4, carbon atoms,a halogen atom, preferably chlorine or bromine, a nitro group, a nitrosogroup, a nitrile group, a phenyl group or a --CO--R¹ group; each R¹ isindependently hydrogen or a hydrocarbyl group having 1 to about 3 carbonatoms; each R² is independently hydrogen or a hydrocarbyl group havingfrom 1 to about 10, preferably from 1 to about 3, carbon atoms, ahalogen atom, preferably chlorine or bromine; each R³ is independentlyhydrogen, or a hydrocarbyl or halohydrocarbyl group having from 1 toabout 6, preferably 1 to about 2 carbon atoms; Q is a direct bond, --CH₂--S--CH₂ --, --(CH₂)_(n") --, or ##STR4## m has an average value fromabout 0.001 to about 6, preferably from about 0.01 to about 3; m' has avalue from 1 to about 10 preferably from about 1 to about 4; n has avalue of zero or one; p has a value from zero to about 30, preferablyfrom zero to about 5; n' has a value from 1 to about 6, preferably 1 toabout 3; n" has an average value from about 1 to about 10; z has a valueof one or two; and p¹ has a value from 1 to about 30, preferably from 1to about 3. The aromatic rings can also contain one or more heteroatomsselected from N, O, S and the like.

The term hydrocarbyl as employed herein means any aliphatic,cycloaliphatic, aromatic, aryl substituted aliphatic or cycloaliphatic,or aliphatic or cycloaliphatic substituted aromatic groups. Thealiphatic or cycloaliphatic groups can be saturated or unsaturated. Whenapplied to the A' group of Formula VI, the hydrocarbyl group can alsocontain one or more heteroatoms selected from N, O, S and the like.Likewise, the term hydrocarbyloxy means a hydrocarbyl group having anoxygen linkage between it and the carbon atom to which it is attached.

Representative of the polyepoxide compounds which are free of mesogenicor rodlike moieties include, for example, the diglycidyl ethers ofresorcinol, 4,4'-isopropylidenediphenol (bisphenol A),4,4'-dihydroxybenzophenone (bisphenol K), 1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol AP), dihydroxydiphenylmethane (bisphenol F),3,3',5,5'-tetrabromobisphenol A, 4,4'-thiodiphenol (bisphenol S),4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl oxide, 3-phenylbisphenolA, 3,3'5,5'-tetrachlorobisphenol A, 3,3'-dimethoxybisphenol A,dipropylene glycol, poly(propylene glycol)s, thiodiglycol; thetriglycidyl ether of tris(hydroxyphenyl)methane; the triglycidyl etherof p-aminophenol; the tetraglycidyl ether of4,4'-diaminodiphenylmethane; the polyglycidyl ether of a phenol orsubstituted phenol-aldehyde condensation product (novolac); thepolyglycidyl ether of a dicyclopentadiene or an oligomer thereof andphenol or substituted phenol condensation product; the advancementreaction products of the aforesaid di- and polyglycidyl ethers witharomatic di- or polyhydroxyl- or di- or polycarboxylic acid containingcompounds including, for example, bisphenol A(4,4'-isopropylidenediphenol), o-, m-, p-dihydroxybenzene,2,4-dimethylresorcinol, 4-chlororesorcinol, tetramethylhydroquinone,1,1-bis(4-hydroxyphenyl)ethane, bis(4,4'-dihydroxyphenyl)methane,4,4'-dihydroxydiphenyl ether, 3,3',5,5'-tetramethyldihydroxydiphenylether, 3,3',5,5'-dichlorodihydroxydiphenyl ether,4,4'-bis(p-hydroxyphenyl isopropyl)diphenyl ether,4,4'-bis(p-hydroxyphenoxy)benzene, 4,4'-bis(p-hydroxyphenoxy)diphenylether, 4,4'-bis(4(4-hydroxyphenoxy)phenyl sulfone)diphenyl ether,4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide,4,4'-dihydroxydiphenyl disulfide, 2,2'-dihydroxydiphenyl sulfone,4,4'-dihydroxydiphenyl methane, 1,1-bis(p-hydroxyphenyl)cyclohexane,4,4'-dihydroxybenzophenone, phloroglucinol, pyrogallol,2,2',5,5'-tetrahydroxydiphenyl sulfone, tris(hydroxyphenyl)methane,dicyclopentadiene diphenol, tricyclopentadiene diphenol, terephthalicacid, isophthalic acid, p-hydroxybenzoic acid; mixtures thereof and thelike.

The epoxy resins containing a mesogenic moiety which can particularly beemployed herein include, for example, those represented by theaforementioned Formulas II, V, VI or IX wherein at least 80 percent ofthe molecules are para substituted by both the bridging groups (--A--)and the substituent containing the glycidyl group(s) ##STR5## as well asthe substituent containing the secondary hydroxy alkylidene group(s)##STR6## which are present when p or p¹ has a value greater than zero.For Formula VI, it is to be understood that para substitution is withrespect to the direct bond between the aromatic rings.

The bridging groups (--A--) in the formulas for the epoxy resinscontaining mesogenic moieties form a rigid central linkage between thearomatic ring pairs, that is, A is a direct single bond, --C.tbd.C--,--CR¹ ═N--, --N═N--, --O--CO--, --NR¹ --CO--, --CR¹ ═N--N═CR¹ --, --CR¹═CR¹ --CO--, --CR¹ ═CR¹ --, --N═CR¹ --, --CO--O--, --CO--NR¹ --,--CO--CR¹ ═CR¹ --, --CO--O--N═CR¹ --, --CR¹ ═N--O--OC--, --CO--NR¹ --NR¹--OC--, --CR¹ ═CR¹ --O--OC--, --CO--O--CR¹ ═CR¹ --, --O--OC--CR¹ ═CR¹--, --CR¹ ═CR¹ --CO--O--, --(CHR¹)_(n') --O--CO--CR¹ ═CR¹ --, --CR¹ ═CR¹--CO--O--(CHR¹)_(n') --, --(CHR¹)_(n') --CO--O-- CR¹ ═CR¹ --, --CR¹ ═CR¹--O--CO--(CHR¹)_(n') --, --CO--S--, --S--OC--, --CH₂ --CH₂ --CO--O--,--O--OC--CH₂ --CH₂ --, --C.tbd.C--C.tbd.C--, --CR¹ ═CR¹ --CR¹ ═CR¹ --,##STR7## group and n, n', z, A¹ and R¹ are as hereinbefore described. Tooptimize the aspect ratio of said mesogenic or rodlike functionalities,it is preferred that the aromatic ring substituents (R in Formulas II,V, VI and IX) are hydrogen or methyl groups.

Representative polyepoxide compounds containing a mesogenic moietyinclude, for example, the diglycidyl ethers of 4,4'-dihydroxybiphenyl,4,4'-dihydroxystilbene, 4,4 '-dihydroxydiphenylacetylene,4,4'-dihydroxydiphenylazomethine, 4,4'-dihydroxyazobenzene,4,4'-dihydroxyazoxybenzene, 4,4'-bis((4-hydroxy)phenoxy)diphenyl,4,4'-dihydroxy-alpha-methylstilbene,3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenyl,3,3',5,5'-tetrachloro-4,4'-dihydroxydiphenyl,2,2',6,6'-tetramethyl-4,4'-dihydroxydiphenyl, 4,4'-dihydroxybenzanilide,4,4'-dihydroxychalcone, 4,4'-dihydroxy-alpha-cyanostilbene,4-hydroxyphenyl-4-hydroxybenzoate,4,4'-dihydroxy-3,3',5,5'-tetrabromo-alpha-methylstilbene,N,N'-bis(4-hydroxyphenyl)terephthalamide, the diglycidyl ethers of thedihydric phenols represented by the following formulas: ##STR8## thetetraglycidyl amines of 4,4'-diamino-alpha-methylstilbene,4,4'-diaminostilbene, 4,4'-diaminobenzanilide, 4,4'-diaminoazobenzene,4,4'-diamino-alpha-cyanostilbene. Also suitable are the productsresulting from advancing the aforementioned diglycidyl ethers witharomatic dihydroxyl or dicarboxylic acid containing compounds including,for example, all of the previously listed diphenol precursors to thediglycidyl ethers containing a mesogenic moiety; mixtures thereof andthe like.

The epoxy resins which can be employed herein can be prepared byreacting the corresponding di- or polyhydroxyl containing compound (oramine containing compound) with an epihalohydrin by any suitable meansknown to those skilled in the art. Suitable such methods are disclosedby Lee and Neville in Handbook of Epoxy Resins, McGraw-Hill, (1967);Japan Kokai Tokyo Koho JP 62 86,484 (87 96, 484); EP 88-008358/92 andJournal of Applied Polymer Science, Vol. 23, 1355-1372 (1972) all ofwhich are incorporated herein by reference.

Generally, the di- or polyhydroxyl containing compound is reacted withan epihalohydrin in the presence of a suitable catalyst and in thepresence or absence of a suitable solvent at a temperature suitably fromabout 0° C. to about 100° C., more suitably from about 20° C. to about80° C., most suitably from about 20° C. to about 65° C.; at pressuressuitably from about 30 mm Hg vacuum to about 100 psia., more suitablyfrom about 30 mm Hg vacuum to about 50 psia., most suitably from aboutatmospheric pressure to about 20 psia.; for a time sufficient tocomplete the reaction, usually from about 1 to about 12, more usuallyfrom about 1 to about 5, most usually from about 1 to about 3 hours; andusing from about 1.5:1 to about 100:1, preferably from about 2:1 toabout 50:1, most preferably from about 3:1 to about 20:1 moles ofepihalohydrin per hydroxyl group. This initial reaction unless thecatalyst is an alkali metal or alkaline earth metal hydroxide employedin stoichiometric quantities produces a halohydrin intermediate which isthen reacted with a basic acting compound to convert the vicinalchlorohydrin groups to epoxide groups. The resultant product is aglycidyl ether compound.

Suitable epihalohydrins which can be employed to prepare the epoxyresins useful in the present invention include, for example, thoserepresented by the following formula ##STR9## wherein R¹ is aspreviously defined; and X' is a halogen. Particularly suitable suchepihalohydrins include, for example, epichlorohydrin, epibromohydrin,epiiodohydrin, methylepichlorohydrin, methylepibromohydrin,methylepiiodohydrin, combinations thereof and the like.

Suitable di- or polyhydroxyl containing compounds (or amine containingcompounds) which can be employed to prepare the epoxy resins useful inthe present invention include, for example, those represented by theformulas ##STR10## wherein R, R², R³, Q, A, A' p¹, m and m' are ashereinbefore defined, and A' in Formula XVI can also contain one or moreheteroatoms selected from N, O, S and the like and may be saturated orunsaturated.

Suitable catalysts which can be employed to prepare the epoxy resinswhich can be employed herein include, for example, ammonium halides suchas, for example, benzyltrimethylammonium chloride,benzyltrimethylammonium bromide, tetrabutylammonium chloride,tetrabutylammonium bromide, tetraoctylammonium chloride,tetraoctylammonium bromide, tetramethylammonium chloride,tetramethylammonium bromide, combinations thereof and the like.

Suitable basic acting compounds which can be employed to prepare theepoxy resins useful herein include, for example, alkali metal oralkaline earth metal hydroxides, carbonates, bicarbonates and the like.Particularly suitable such compounds include, for example, sodiumhydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide,barium hydroxide, magnesium hydroxide, manganese hydroxide, sodiumcarbonate, potassium carbonate, lithium carbonate, calcium carbonate,barium carbonate, magnesium carbonate, manganese carbonate, sodiumbicarbonate, potassium bicarbonate, lithium bicarbonate, calciumbicarbonate, barium bicarbonate, magnesium bicarbonate, manganesebicarbonate, mixtures, thereof and the like. Most preferred is sodiumhydroxide or potassium hydroxide.

Suitable solvents which can be employed herein include, for example,alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, glycol ethers,amides, sulfoxides, sulfones, combinations thereof and the like.Particularly suitable solvents include, for example, methanol, ethanol,isopropanol, hexane, heptane, octane, nonane, decane, toluene, xylene,ethylene glycol methyl ether, ethylene glycol ethyl ether, ethyleneglycol n-butyl ether, ethylene glycol phenyl ether, propylene glycolmethyl ether, propylene glycol phenyl ether, tripropylene glycol methylether, diethylene glycol methyl ether, diethylene glycol ethyl ether,diethylene glycol n-butyl ether, diethylene glycol phenyl ether,butylene glycol methyl ether, N,N-dimethylformamide,N-methylpyrrolidinone, N,N-dimethylacetamide, dimethylsulfoxide,sulfolane, combinations thereof and the like.

The solvent is usually employed in amounts suitably from about 5 toabout 95, more suitably from about 20 to about 60, most suitably fromabout 30 to about 40, percent by weight based upon the combined weightof solvent and epihalohydrin.

For the production of epoxy resins from di- and polyhydroxyl containingcompounds (or amine containing compounds) possessing functional groupsor linkages that are sensitive to hydrolysis under the reactionconditions employed in certain of the epoxidation chemistries, alternatetechniques of preparation may be employed. As a typical example, U.S.Pat. No. 4,762,901 teaches preparation of the diglycidyl ether of thebiphenol represented by the following formula ##STR11## which is acompound containing an ester linkage known to be sensitive tohydrolysis, using an anhydrous epoxidation technique. This techniqueemploys azeotropic removal of water/epichlorohydrin concurrent with thecontrolled addition of aqueous sodium hydroxide to a reaction mixtureconsisting of epichlorohydrin, a diphenol, a phase transfer catalystsuch as, for example, benzyltrimethylammonium chloride, and optionallysolvent(s). It is advantageous to conduct such anhydrous epoxidationreactions under a vacuum to facilitate the azeotropic removal of water.It is also operable and advantageous to utilize sodium hydroxide free ofwater as the alkali metal hydroxide reactant. In order to controlreaction exotherm, the solid sodium hydroxide is typically added inaliquots as a powder to the epoxidation reaction mixture. A typicalanhydrous epoxidation technique is described in U.S. Pat. No. 4,499,255which is incorporated herein by reference in its entirety.

Another specific anhydrous epoxidation technique involves catalyticcoupling of the di- or polyhydroxyl containing compound with anepihalohydrin, typically using as a catalyst one or more of theaforementioned ammonium halides. The resultant solution of halohydrin inexcess epihalohydrin is then treated with finely pulverized potassiumcarbonate to effect dehydrohalogenation to the epoxy resin.

Advancement reaction of di- and polyglycidyl ethers can be performed bythe known methods described in the aforementioned Handbook of EpoxyResins. This usually includes combining one or more suitable compoundshaving an average of more than one active hydrogen atom per molecule,including, for example, dihydroxy aromatic, dithiol or dicarboxylic acidcompounds or compounds containing one primary amine or amide group ortwo secondary amine groups and the di- or polyglycidyl ethers with theapplication of heat and mixing to effect the advancement reaction. Acatalyst is frequently added to facilitate the advancement reaction.

The advancement of the epoxy resins containing one or more mesogenicmoieties with compounds having an average of more than one activehydrogen per molecule is employed to linearly chain extend the resin soas to produce an advanced epoxy resin. This linear chain extension isrequired for some mesogen-containing resin compositions in order toobtain liquid crystal character. The advancement of the mesogenic epoxyresins can also be used to increase the temperature range in which aparticular resin is liquid crystalline and to control the degree ofcrosslinking during the final curing stage.

The epoxy resin containing one or more mesogenic or rodlike moieties andthe compound having an average of more than one active hydrogen atom permolecule are reacted in amounts which provide suitably from about 0.01:1to about 0.99:1, more suitably from about 0.05:1 to about 0.9:1, mostsuitably from about 0.10:1 to about 0.50:1 active hydrogen atoms perepoxy group.

Particularly suitable compounds having an average of more than oneactive hydrogen atom per molecule which can be employed herein in thepreparation of the advanced epoxy resins include hydroxyl-containingcompounds, carboxylic acid-containing compounds and primaryamine-containing compounds.

Particularly suitable hydroxyl-containing compounds include, forexample, hydroquinone, bisphenol A, 4,4'-dihydroxydiphenylmethane,4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl oxide,4,4'-dihydroxybenzophenone, 1,1-bis(4-hydroxyphenyl)-1-phenylethane,3,3',5,5'-tetrachlorobisphenol A, 3,3'-dimethoxybisphenol A,4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-α,α'-diethylstilbene,4,4'-dihydroxy-α-methylstilbene, 4,4'-dihydroxybenzanilide,4,4'-dihydroxy-2,2'-dimethylazoxybenzene,4,4'-dihydroxy-α-cyanostilbene, bis(4-hydroxyphenyl)terephthalate,bis(N,N'-4-hydroxyphenyl)terephthalamide,bis(4'-hydroxybiphenyl)terephthalate, 4,4'-dihydroxyphenylbenzoate,bis(4'-hydroxyphenyl)-1,4-benzenediimine,4,4"-dihydroxybiphenylbenzoate,1,4-bis(4'-hydroxyphenyl-1'-carboxamide)benzene,1,4-bis(4'-hydroxyphenyl-1'-carboxy)benzene,4,4'-bis(4"-hydroxyphenyl-1"-carboxy)biphenyl, mixtures thereof and thelike.

Particularly suitable carboxylic acid-containing compounds include, forexample, terephthalic acid, 4,4'-benzanilide dicarboxylic acid,4,4'-phenylbenzoate dicarboxylic acid, 4,4'-stilbene-dicarboxylic acidand mixtures thereof and the like.

Particularly suitable primary amine-containing compounds include, forexample, aniline, 4'-sulfonamido-N-phenyl benzamide,4'-sulfonamido-N'-phenyl-4-chlorobenzamide, 4-amino-1-phenylbenzoate,4-amino-N-phenylbenzamide, N-phenyl-4-amino-phenyl-1-carboxamide,phenyl-4-aminobenzoate, biphenyl-4-aminobenzoate,1-phenyl-4'-aminophenylterephthalate, mixtures thereof and the like.

The advancement reaction can be conducted in the presence of a suitableadvancement catalyst such as, for example, phosphines, quaternaryammonium compounds, phosphonium compounds, tertiary amines and the like.Particularly suitable catalysts include, for example,ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide,ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium diacetate(ethyltriphenylphosphonium acetate.acetic acid complex),ethyltriphenylphosphonium phosphate, tetrabutylphosphonium chloride,tetrabutylphosphonium bromide, tetrabutylphosphonium iodide,tetrabutylphosphonium diacetate (tetrabutylphosphonium acetate.aceticacid complex), butyltriphenylphosphonium tetrabromobisphenate,butyltriphenylphosphonium bisphenate, butyltriphenylphosphoniumbicarbonate, benzyltrimethylammonium chloride, tetramethylammoniumhydroxide, triethylamine, tripropylamine, tributylamine,2-methylimidazole, benzyldimethylamine, mixtures thereof and the like.Many of these catalysts are described in U.S. Pat. Nos. 3,306,872;3,341,580; 3,379,684; 3,477,990; 3,547,881; 3,637,590; 3,843,605;3,948,855; 3,956,237; 4,048,141; 4,093,650; 4,131,633; 4,132,706;4,171,420; 4,177,216; and 4,366,295, all of which are incorporatedherein by reference.

The amount of advancement catalyst depends, of course, upon theparticular reactants and catalyst employed; however, it is usuallyemployed in quantities of from about 0.03 to about 3, preferably fromabout 0.03 to about 1.5, most preferably from about 0.05 to about 1.5percent by weight based upon the weight of the epoxy containingcompound.

The advancement reaction can be conducted at atmospheric,superatmospheric or subatmospheric pressures at temperatures of fromabout 20° C. to about 260° C., preferably from about 80° C. to about240° C., more preferably from about 100° C. to about 200° C. The timerequired to complete the advancement reaction depends upon thetemperature employed. Higher temperatures require shorter periods oftime whereas lower temperatures require longer periods of time.Generally, however, times of from about 5 minutes to about 24 hours,preferably from about 30 minutes to about 8 hours, more preferably fromabout 30 minutes to about 3 hours are suitable.

If desired, the advancement reaction can be conducted in the presence ofone or more solvents. For the production of advanced epoxy resins usinga reactant which is of low solubility in the di- or polyglycidyl etherreactant, it is frequently of advantage to add one or more solvents tothe reaction mixture. Suitable such solvents include, for example,glycol ethers, aliphatic and aromatic hydrocarbons, aliphatic ethers,cyclic ethers, ketones, esters, amides, combinations thereof and thelike. Particularly suitable solvents include, for example, toluene,benzene, xylene, methyl ethyl ketone, methyl isobutyl ketone, diethyleneglycol methyl ether, dipropylene glycol methyl ether, dimethylformamide,dimethylsulfoxide, N-methypyrrolidinone, tetrahydrofuran, propyleneglycol methyl ether, combinations thereof and the like. The solvents canbe employed in amounts of from about zero to about 80%, preferably fromabout 20% to about 60%, more preferably from about 30% to about 50% byweight based upon the weight of the reaction mixture. Care should betaken to utilize only those solvents which are inert to reaction withany of the reactants employed in the advancement reaction or the productformed therefrom.

Single Active Hydrogen and Nitro (Nitroso) Group Containing Component

Materials containing a single active hydrogen which is reactive with anepoxide group and one or more nitro (nitroso) groups useful in thepreparation of the nitro (nitroso) group terminated epoxy resin adductscontaining one or more mesogenic moieties of the present inventioninclude the nitro and nitroso phenols, such as, for example, thoserepresented by Formula XX where Y is a --OH group and one or more of thegroups represented by R is a nitro or nitroso group and by Formulas XXI,XXIII and XIV, where one Y is a --OH group and the other Y becomes a Rgroup and one or more of the groups represented by R is a nitro ornitroso group and by Formula XXII where one Y is a --OH group and theother two Y groups become R groups and one or more of the groupsrepresented by R is a nitro or nitroso group; the nitro and nitrosocarboxylic acids, such as, for example, those represented by Formula XXwhere Y is a --COOH group and one or more of the groups represented by Ris a nitro or nitroso group and by Formulas XXI, XXIII and XIV, whereone Y is a --COOH group and the other Y becomes a R group and one ormore of the groups represented by R is a nitro or nitroso group and byFormula XXII where one Y is a --COOH group and the other two Y groupsbecome R groups and one or more of the groups represented by R is anitro or nitroso group; the nitro and nitroso mercaptans, such as, forexample, those represented by Formula XX where Y is a --SH group and oneor more of the groups represented by R is a nitro or nitroso group andby Formulas XXI, XXIII and XIV, where one Y is a --SH group and theother Y becomes a R group and one or more of the groups represented by Ris a nitro or nitroso group and by Formula XXII where one Y is a --SHgroup and the other two Y groups become R groups and one or more of thegroups represented by R is a nitro or nitroso group; the nitro andnitroso secondary monoamines, such as, for example, those represented byFormula XX where Y is a --NHR⁴ group and the other Y becomes a R groupand one or more of the groups represented by R is a nitro or nitrosogroup and by Formulas XXI, XXIII and XIV, where one Y is a --NHR⁴ groupand the other Y becomes a R group and one or more of the groupsrepresented by R is a nitro or nitroso group and by Formula XXII whereone Y is a --NHR⁴ group and the other two Y groups become R groups andone or more of the groups represented by R is a nitro or nitroso groupand R⁴ is a hydrocarbyl group having from 1 to about 12, preferably from1 to about 2 carbon atoms; wherein R, R², A, A', n, and p¹ are ashereinbefore defined, and in Formula XXIV, A' can also contain one ormore heteroatoms selected from N, O, S and the like and may be saturatedor unsaturated. ##STR12##

Representative of the nitro and nitroso phenols which are free ofmesogenic moieties include, for example, o-, m-, p-nitrophenol, o-, m-,p-nitrosophenol, 3-methyl-4-nitrophenol, 3,5-dimethyl-4-nitrophenol,3-chloro-4-nitrophenol, 4-nitro-4'-hydroxydiphenyl methane,4-nitro-4'-hydroxydiphenyl oxide, 4-nitro-4'-hydroxydiphenyl sulfone,(4-nitrophenyl)(4-hydroxyphenyl)methanone, mixtures thereof and thelike.

Representative of the nitro and nitroso phenols containing one or moremesogenic moieties include, for example, 4-hydroxy-4'-nitrodiphenyl,4-hydroxy-4'-nitrosodiphenyl, 4-hydroxy-4'-nitrostilbene,4-hydroxy-4'-nitrodiphenylazomethine, 4-hydroxy-4'-nitroazoxybenzene,4-hydroxy-4'-nitrochalcone, 4-hydroxy-4'-nitrodiphenylacetylene,4-hydroxy-4'-nitrobenzanilide, 4-nitro-4'-hydroxybenzanilide,4-hydroxyphenyl-4'-nitrobenzoate,4-hydroxy-4'-nitro-alpha-cyanostilbene,4-hydroxy-4'-nitro-alpha-chlorostilbene,4-hydroxy-4'-nitro-alpha-methylstilbene,3,3'-dimethyl-4-hydroxy-4'-nitrodiphenyl, mixtures thereof and the like.

Representative of the nitro and nitroso carboxylic acids which are freeof mesogenic moieties include, for example, o-, m-, p-nitrobenzoic acid,o-, m-, p-nitrosobenzoic acid, 3-methyl-4-nitrobenzoic acid,3,5-dimethyl-4-nitrobenzoic acid, 3-chloro-4-nitro-benzoic acid,4-nitro-4'-carboxydiphenyl methane 4-nitro-4'-carboxydiphenyl oxide,4-nitro-4'-carboxydiphenyl sulfone,(4-nitrophenyl)(4-carboxyphenyl)methanone, mixtures thereof and thelike.

Representative of the nitro and nitroso carboxylic acids containing oneor more mesogenic moieties include, for example,4-carboxy-4'-nitrobiphenyl, 4-carboxy-4'-nitrosodiphenyl,4-carboxy-4'-nitrostilbene, 4-carboxy-4'-nitrodiphenylazomethine,4-carboxy-4'-nitroazoxybenzene, 4-carboxy-4'-nitro-chalcone,4-carboxy-4'-nitrodiphenylacetylene, 4-carboxy-4'-nitrobenzanilide,4-nitro-4'-carboxybenzanilide, 4-carboxyphenyl-4'-nitrobenzoate,4-carboxy-4'-nitro-alpha-cyanostilbene,4-carboxy-4'-nitro-alpha-chlorostilbene,4-carboxy-4'-nitro-alpha-methylstilbene,3,3'-dimethyl-4-carboxy-4'-nitrodiphenyl, mixtures thereof and the like.

Representative of the nitro and nitroso mercaptans which are free ofmesogenic moieties include, for example, o-, m-, p-nitrobenzenethiol,o-, m-, p-nitrosobenzenethiol, 3-methyl-4-nitrobenzenethiol,3,5-dimethyl-4-nitrobenzenethiol, 3-chloro-4-nitrobenzenethiol,4-nitro-4'-mercaptodiphenyl methane, 4-nitro-4'-mercaptodiphenyl oxide,4-nitro-4'-mercaptodiphenyl sulfone,(4-nitrophenyl)(4-mercaptophenyl)methanone, mixtures thereof and thelike.

Representative of the nitro and nitroso mercaptans containing one ormore mesogenic moieties include, for example,4-mercapto-4'-nitrodiphenyl, 4-mercapto-4'-nitrosodiphenyl,4-mercapto-4'-nitrostilbene, 4-mercapto-4'-nitrodiphenylazomethine,4-mercapto-4'-nitroazoxybenzene, 4-mercapto-4'-nitrochalcone,4-mercapto-4'-nitrodiphenylacetylene, 4-mercapto-4'-nitrobenzanilide,4-nitro-4'-mercaptobenzanilide, 4-mercaptophenyl-4 '-nitrobenzoate,4-mercapto-4'-nitro-alpha-cyanostilbene,4-mercapto-4'-nitro-alpha-chlorostilbene,4-mercapto-4'-nitro-alpha-methylstilbene,3,3'-dimethyl-4-mercapto-4'-nitrodiphenyl, mixtures thereof and thelike.

Representative of the nitro and nitroso secondary monoamines which arefree of mesogenic moieties include, for example, o-, m-,p-nitro-N-methylaniline, o-, m-, p-nitro-N-ethylaniline, o-, m-,p-nitroso-N-methylaniline, 3-methyl-4-nitro-N-methylaniline,3,5dimethyl-4-nitro-N-methylaniline, 3-chloro-4-nitro-N-methylaniline,4-nitro-4'-N-methylaminodiphenyl methane,4-nitro-4'-N-methylaminodiphenyl oxide, 4-nitro-4'-N-methylaminodiphenylsulfone, (4-nitrophenyl)(4-N-methylaminophenyl)methanone, mixturesthereof and the like.

Representative of the nitro and nitroso secondary monoamines containingone or more mesogenic moieties include, for example,4-N-methylamino-4'-nitrodiphenyl, 4-N-ethylamino-4'-nitrodiphenyl,4-N-methylamino-4'-nitrosodiphenyl, 4-N-methylamino-4'-nitrostilbene,4-N-methylamino-4'-nitrodiphenylazomethine,4-N-methylamino-4'-nitroazoxybenzene, 4-N-methylamino-4'-nitrochalcone,4-N-methylamino-4'-nitrodiphenylacetylene,4-N-methylamino-4'-nitrobenzanilide,4-nitro-4'-N-methylaminobenzanilide,4-N-methylaminophenyl-4'-nitrobenzoate,4-N-methylamino-4'-nitro-alpha-cyanostilbene,4-N-methylamino-4'-nitro-alpha-chlorostilbene,4-N-methylamino-4'-nitro-alpha-methylstilbene,3,3'-dimethyl-4-N-methylamino-4'-nitrodiphenyl, mixtures thereof and thelike.

Nitro(Nitroso) Group Terminated Adducts

The adducts containing terminating nitro(nitroso) groups and one or moremesogenic moieties of the present invention are prepared by reacting (B)one or more materials containing one hydrogen which is reactive with anepoxide group selected from the group consisting of (1) nitro andnitroso phenols, (2) nitro and nitrosocarboxylic acids, (3) nitro andnitrosomercaptans, (4) nitro and nitroso secondary monoamines (5)mixtures thereof with one or more (A) epoxy resins in an amountsufficient to provide from about 1:1 to about 100:1, preferably fromabout 1:1 to about 20:1, most preferably from about 1:1 to 2:1equivalents of hydrogen reactive with an epoxide group (excludingsecondary hydroxyl groups formed by epoxide ring opening reaction toform the adduct) per equivalent of epoxide reacted, with the provisothat one or more mesogenic moieties are present in either (A) the epoxyresin reactant or (B) the material containing one hydrogen which isreactive with an epoxide group or in both (A) and (B).

The term "reactive with an epoxide group", as employed in thepreparation of the adduct means reactive at the conditions employed toprepare the adduct. There may be present hydrogen atoms which arenon-reactive with the epoxide group at the conditions employed toprepare the adduct, but which are reactive at conditions at which anepoxy resin is cured with the resultant adduct. In which case, thehydrogen atoms which are not reactive with the epoxy resin at theconditions at which the adduct is prepared are not considered in theaforementioned reactive hydrogen to epoxide ratios.

The term "epoxy resin adduct" as used herein includes the epoxy resinwherein the terminal epoxide groups have been reacted in a ring openingreaction with the material containing one hydrogen which is reactivewith an epoxide group to give the characteristic 2-hydroxypropylfunctionality as a linkage between the residual epoxy resin structureand the residual structure from the material containing one hydrogenwhich is reactive with an epoxide group. A typical example is thereaction product of p-nitrophenol and the diglycidyl ether of4,4'-dihydroxy-alpha-methylstilbene: ##STR13##

The adduct may also contain unreacted material containing one hydrogenwhich is reactive with an epoxide group. Thus in the case of thereaction between p-nitrophenol and the diglycidyl ether of4,4'-dihydroxy-alpha-methylstilbene, if stoichiometric excess ofp-nitrophenol is employed and not removed, it thus becomes a part of theepoxy resin adduct. The adduct may also contain branched or crosslinkedstructure derived from reaction between an epoxide group and thehydroxyl group of a 2-hydroxypropyl linkage contained in said adduct. Atypical example is the reaction of a backbone hydroxyl group of theepoxy resin adduct of p-nitrophenol and the diglycidyl ether of4,4'-dihydroxy-alpha-methylstilbene with an epoxide group from a secondmolecule of the diglycidyl ether of 4,4'-dihydroxy-alpha-methylstilbenewhich has already been adducted with p-nitrophenol at one epoxide groupof the molecule: ##STR14##

Minor amounts of other structures may be present in the adducts of thepresent invention, for example, those which may be present in the epoxyresin reactant, such as, the 1,2-glycol group derived from hydrolysis ofthe epoxide group, or halomethyl groups caused by addition ofepihalohydrin to the hydroxyl group of an intermediate halohydrinmolecule.

A catalyst is optionally employed to prepare the nitro (nitroso) groupterminated adducts containing one or more mesogenic moieties of thepresent invention. Suitable catalysts include the aforementionedphosphines, quaternary ammonium compounds, phosphonium compounds,tertiary amines, mixtures thereof and the like. The amount of catalystused, if any, depends upon the particular reactants and catalystemployed; however, it is usually employed in quantities from about 0.01to about 3, preferably from about 0.01 to about 1.5, most preferablyfrom about 0.03 to about 0.75 percent by weight based upon the weight ofthe epoxy containing compound.

Reaction conditions for forming the nitro (nitroso) group terminatedadducts containing one or more mesogenic moieties of the presentinvention vary widely depending upon the type and amount of reactantsemployed, the type and amount of catalyst used, if any, the use ofsolvent(s), the mode of addition of the reactants employed, and otherknown variables. Thus, the reaction may be conducted at atmospheric,superatmospheric or subatmospheric pressures at temperatures of fromabout 0° C. to about 260° C., preferably from about 20° C. to about 200°C., most preferably from about 35° C. to about 160° C. The time requiredto complete the reaction depends not only upon the aforementionedvariables, but also upon the temperature employed. Higher temperaturesrequire shorter periods of time whereas lower temperatures requirelonger periods of time. Generally, however, times of from about 5minutes to about one week, more preferably from about 30 minutes toabout 72 hours, most preferably from about 60 minutes to about 48 hoursare suitable.

The reaction to form the nitro (nitroso) group terminated adductscontaining one or more mesogenic moieties of the present invention maybe conducted in the presence of one or more solvents. Solvents may bebeneficially employed, for example, to improve the solubility of one ormore reactants in the reactant mixture, to dissolve a solid reactantthus rendering it easier to meter into the reaction, or to dilute theconcentration of reacting species as a means to moderate the adductforming reaction and thus vary the distribution of components comprisingthe adduct. Suitable solvents include those which are substantiallyinert to reaction with any of the reactants employed or the adductproduct formed therefrom. Thus the solvents and amounts of said solventspreviously described for the advancement reaction are generally suitablefor use in the adduct forming reaction.

The contacting together of (A) one or more epoxy resins and (B) one ormore materials containing one hydrogen which is reactive with an epoxidegroup selected from the group consisting of (1) nitro andnitrosophenols, (2) nitro and nitrosocarboxylic acids, (3) nitro andnitrosomercaptans, (4) nitro and nitroso secondary monoamines, (5)mixtures thereof with the proviso that one or more mesogenic moietiesmay be present in (A) the epoxy resin reactant or (B) the materialcontaining one hydrogen which is reactive with an epoxide group or inboth (A) and (B) may be done in any configuration which provides anadduct that is essentially free of epoxide groups. Thus, the epoxy resincomponent and the material containing one hydrogen which is reactivewith an epoxide group may be directly mixed together and subjected tothe aforesaid conditions conducive to reaction, or one component may beadded to the other component in increments including up to continuousaddition. If increments are added, all or a part of an added incrementmay be allowed to react prior to addition of the next increment.

Various post treatments may be applied to the nitro (nitroso) groupterminated adducts containing one or more mesogenic moieties of thepresent invention as a means to vary the distribution of componentscomprising the adduct, to modify the reactivity of the adduct with anepoxy resin, to modify the physical state of the adduct, or for otherknown reasons. As a specific example, in the preparation of the adductof p-nitrophenol and the diglycidyl ether of4,4'-dihydroxy-alpha-methylstilbene, a large stoichiometric excess ofphenolic hydroxyl groups derived from the p-nitrophenol, with respect toepoxide groups derived from the diglycidyl ether of4,4'-dihydroxy-alpha-methylstilbene may be used, however, the finishedreaction product now contains, as a part of the adduct composition, ahigh concentration of p-nitrophenol as the unreacted material containingone hydrogen which is reactive with an epoxide group and one or morenitro (nitroso) groups. In the method of the present invention, posttreatment of the adduct via vacuum distillation to strip out theunreacted p-nitrophenol may be employed. Many other alternate methods ofpost treatment to vary the distribution of the components comprising theadducts of the present invention may be employed, such as, for example,recrystallization, sublimation, chromatographic separation, zonerefining, crystal refining, wiped film distillation, extraction,preferential chemical derivatization of one or more components of saidadduct followed by its removal, combinations thereof and the like.Another class of post treatments of the adducts of the present inventioninvolves the addition of one or more components to the epoxy resinadduct to modify one or more properties of said adduct. For example, oneor more accelerators or retarding agents may be blended with the adduct,wherein the nitro groups therein have been reduced to primary aminegroups, to modify its subsequent reactivity in curing of an epoxy resin.As a second example, one or more epoxy resin curing agents, such as, forexample, those delineated herein may be added to the finished adductwherein the nitro groups therein have been reduced.

Amine Group Terminated Adducts

The nitro (nitroso) group terminated adducts of the present inventionmay be reduced to amine terminated adducts. Suitable methods for thereduction of nitro and nitroso compounds to amines are disclosed byMarch in Advanced Organic Chemistry, John Wiley and Sons, pages 1103 to1106 (1985) which is incorporated herein by reference. The generalmethods for the reduction reaction include the use of iron, zinc or tinplus a mineral acid, catalytic hydrogenation, for example in thepresence of platinum, AlH₃ --AlCl₃, hydrazine plus catalyst,dodecacarbonyltriiron-methanol, TiCl₃, hot liquid paraffin, formic acidand palladium on carbon, sulfides such as NaHS, and sodiumdihydro(trithio)borate. For the reduction of nitro (nitroso) groupterminated adducts possessing functional groups or linkages that aresensitive to reduction under the reaction conditions employed in certainof the reduction chemistries, alternate techniques of preparation may beemployed. As a typical example, U.S. Pat. Nos. 3,845,018 and 3,975,444teach the reduction of aromatic nitro compounds containing the acetylenegroup, a group sensitive to reduction. The techniques reported thereinemploy aqueous ferrous sulfate heptahydrate and ammonium hydroxide,aqueous sodium hydrosulfite and potassium carbonate solution, orpowdered zinc in ammonium hydroxide. As a second example, Ram andEhrenkaufer, Tetrahedron Letters, volume 25, number 32, pages 3415 to3418 (1984) teach the reduction of aromatic nitro compounds containingthe cyano group, a group sensitive to reduction. The technique reportedtherein employs palladium on carbon with anhydrous ammonium formate. Theaforementioned references are incorporated herein in their entirety.

Functionalized Adducts

The nitro (nitroso) group terminated adducts of the present inventionmay be partially or totally functionalized via reaction of a part or allof the backbone aliphatic hydroxyl groups contained therein. Suitablemethods for the partial or total functionalization of said backbonealiphatic hydroxyl groups include, for example, etherification,esterification, halogenation, urethanation, oxidation/reduction methods,and the like. Thus, reaction of the hydroxyl groups with a dialkylsulfate or a alkyl halide, such as, for example, dimethyl sulfate ormethyl iodide, provides the etherified nitro (nitroso) group terminatedadduct. As a typical example, Furniss, Hannaford, Rogers, Smith andTatchell, Vogel's Handbook of Practical Organic Chemistry, Longman,Inc., page 472 (1978) teach etherification of the aliphatic hydroxylgroup via reaction with dimethyl sulfate and aqueous sodium hydroxide.Reaction of the hydroxyl groups with an acid anhydride or an acylhalide, such as, for example, acetic anhydride or acetyl chloride,provides the esterified nitro (nitroso) group terminated adduct. As atypical example, the aforementioned Furniss, et al. reference, pages 511to 512 teaches etherification of the aliphatic hydroxyl group viareaction with acetyl chloride in the presence of dimethylaniline orreaction with acetic anhydride in the presence of anhydrous zincchloride catalyst. In a reaction similar to esterification of thealiphatic hydroxyl group with an acyl halide, a chloroformate may beused to form the carbonate. Displacement reaction of the hydroxyl groupswith a halogen halide or thionyl halide, such as, for example, hydrogenbromide or thionyl chloride, provides the halogenated nitro (nitroso)group terminated adduct. As a typical example, the aformentionedFurniss, et al. reference, pages 381 to 389 teaches halogenation of thealiphatic hydroxyl group via reaction with hydrogen chloride (bromide)or thionyl chloride. Reaction of the hydroxyl groups with amonoisocyanate, such as, for example, methyl or phenyl isocyanate,provides the urethane functionalized nitro (nitroso) group terminatedadduct. Reaction of aliphatic hydroxyl groups with isocyanates to formthe urethane structure is taught by Oertel, Polyurethane Handbook,Hanser Publishers, page 11 (1985) and typically involves the simplecontacting together of the compounds containing the hydroxyl andisocyanate groups, optionally in the presence of a catalyst, such as,for example, stannous octoate. Oxidation of the hydroxyl groups, forexample by sodium dichromate in dilute sulfuric acid or by an aluminumalkoxide in excess acetone, provides the ketone functionalized nitrogroup terminated adduct. As a typical example, the aformentionedFurniss, et al. reference, pages 425 to 429 teaches oxidation ofsecondary aliphatic hydroxyl groups with aqueous chromic acid in a twophase diethylether-water system or aluminum t-butoxide and acetone.Reduction of the ketone groups, for example using the Huang-Minlonmodification of the Wolff-Kishner reaction, provides the alkanefunctionalized nitro group terminated adduct. As a typical example, theaforementioned Furniss, et al. reference, pages 600 to 601, 605 to 606teaches reduction of ketone groups using hydrazine hydrate and potassiumhydroxide.

Thermosettable (Curable) Mixtures

The thermosettable mixtures of the present invention are prepared bymixing together one or more of the amine terminated adducts containingone or more mesogenic moieties with one or more epoxy resins, all, none,or a part of which may contain one or more mesogenic or rodlikemoieties. The amine terminated adducts are employed in amounts whichwill effectively cure the mixture, with the understanding that theseamounts will depend upon the particular adduct and epoxy resin employed.Generally, suitable amounts of the adduct include amounts which willprovide from about 0.80:1 to about 1.50:1 equivalents of amine hydrogenwhich is reactive with an epoxide group per equivalent of epoxide groupin the epoxy resin at the conditions employed for curing.

The application of heat or a combination of heat and pressure may beemployed in the curing of the thermosettable mixtures of the presentinvention. Temperatures employed can vary over a considerable range butare usually in the range of 20° C. to 250° C. Depending upon therelative solubility and phase transition temperature(s) associated withthe mesogenic moieties present in the thermosettable compositions,curing at an elevated temperature can be especially desirable to enhancethe molecular anisotropy of the cured product.

The thermosettable mixtures of the present invention may also containone or more of the known curing agents for epoxy resins such as, forexample, primary and secondary polyamines, carboxylic acids andanhydrides thereof, aromatic hydroxyl containing compounds, imidazoles,guanidines, urea-aldehyde resins, alkoxylated urea-aldehyde resins,melamine-aldehyde resins, alkoxylated melamine-aldehyde resins,aliphatic amines, cycloaliphatic amines, aromatic amines, epoxy resinadducts free of mesogenic or rodlike moieties, combinations thereof andthe like. Particularly suitable curing agents include, for example,methylenedianiline, 4,4'-diaminostilbene, 4,4'-diaminobenzanilide,4,4'-diamino-alpha-methylstilbene, dicyandiamide, ethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,urea-formaldehyde resins, melamine-formaldehyde resins, methylolatedurea-formaldehyde resins, methylolated melamine-formaldehyde resins,phenol-formaldehyde novolac resins, sulfanilamide,diaminodiphenylsulfone, diethyltoluenediamine, t-butyltoluenediamine,bis-4-aminocyclohexylmethane, isophoronediamine, diaminocyclohexane,hexamethylenediamine, piperazine, aminoethylpiperazine,2,5-dimethyl-2,5-hexanediamine, 1,12-dodecanediamine,tris-3-aminopropylamine, combinations thereof and the like. If used as acomponent of the thermosettable mixtures of the present invention, fromabout 1 to about 99, preferably from about 1 to about 40, mostpreferably from about 1 to about 20 percent of the equivalents ofhydrogen which are reactive with an epoxide group provided by the adductcontaining one or more mesogenic moieties are substituted out by usingone or more of the aforesaid curing agents.

Orientation

During processing prior to curing and/or during cure of the curableepoxy resin compositions into a part, electric or magnetic fields orshear stresses can be applied for the purpose of orienting the mesogenicor rodlike moieties contained or developed therein which in effectimproves the mechanical properties. As specific examples of thesemethods, Finkelmann, et al, Macromol. Chem., 180, 803-806 (March 1979)induced orientation in thermotropic methacrylate copolymers containingmesogenic side chain groups decoupled from the main chain via flexiblespacers in an electric field. Orientation of mesogenic side chain groupsdecoupled from the polymer main chain via flexible spacers in a magneticfield has been demonstrated by Roth and Kruecke, Macromol. Chem., 187,2655-2662 (November 1986). Magnetic field induced orientation ofmesogenic main chain containing polymers has been demonstrated by Moore,et al, ACS Polymeric Material Sciences and Engineering, 52, 84-86(April-May 1985). Magnetic and electric field orientation of lowmolecular weight mesogenic compounds is discussed by W. R. Krigbaum inPolymer Liquid Crystals, pages 275-309 (1982) published by AcademicPress, Inc. All of the above are incorporated herein by reference intheir entirety.

In addition to orientation by electric or magnetic fields, polymericmesophases can be oriented by drawing and/or shear forces which areinduced by flow through dies, orifices, and mold gates. A generaldiscussion for orientation of thermotropic liquid crystal polymers bythis method is given by S. K. Garg and S. Kenig in High ModulusPolymers, pages 71-103 (1988) published by Marcel Dekker, Inc. which isincorporated herein by reference. For the mesomorphic systems based onthe epoxy resin compositions, this shear orientation can be produced byprocessing methods such as injection molding, extrusion, pultrusion,filament winding, filming and prepreging.

The thermosettable mixtures of the present invention can be blended withother materials such as solvents or diluents, fillers, pigments, dyes,flow modifiers, thickeners, reinforcing agents, mold release agents,wetting agents, stabilizers, fire retardant agents, surfactants,combinations thereof and the like.

These additives are added in functionally equivalent amounts, e.g., thepigments and/or dyes are added in quantities which will provide thecomposition with the desired color; however, they are suitably employedin amounts of from about zero to about 20, more suitably from about 0.5to about 5, most suitably from about 0.5 to about 3 percent by weightbased upon the weight of the total blended composition.

Solvents or diluents which can be employed herein include, for example,hydrocarbons, ketones, glycol ethers, aliphatic ethers, cyclic ethers,esters, amides, monoepoxides, combinations thereof and the like.Particularly suitable solvents or diluents include, for example,toluene, benzene, xylene, methyl ethyl ketone, methyl isobutyl ketone,diethylene glycol methyl ether, dipropylene glycol methyl ether,dimethylformamide, N-methylpyrrolidinone, tetrahydrofuran, propyleneglycol methyl ether, 4-tertiary-butylphenyl glycidyl ether, cresylglycidyl ether, epoxidized soybean oil, combinations thereof and thelike.

The modifiers such as thickeners, flow modifiers and the like can besuitably employed in amounts of from zero to about 10, more suitablyfrom about 0.5 to about 6, most suitably from about 0.5 to about 4percent by weight based upon the weight of the total composition.

Reinforcing materials which can be employed herein include natural andsynthetic fibers in the form of woven fabric, mats, monofilament,multifilament, unidirectional fibers, rovings, random fibers orfilaments, inorganic fillers of whiskers, hollow spheres, and the like.Suitable reinforcing materials include, glass, ceramics, nylon, rayon,cotton, aramid, graphite, polyalkylene terephthalates, polyethylene,polypropylene, polyesters, combinations thereof and the like.

Suitable fillers which can be employed herein include, for example,inorganic oxides, ceramic microspheres, plastic microspheres, glassmicrospheres, inorganic whiskers, CaCO₃, combinations thereof and thelike.

The fillers can be employed in amounts suitable from about zero to about95, more suitably from about 10 to about 80, most suitably from about 40to about 60 percent by weight based upon the weight of the totalcomposition.

The compositions of the present invention are useful in, but not limitedto, applications such as coatings, encapsulations, extrusions, moldings,films, pultrusions, electrical and structural laminates or composites,and the like. In some instances, they can be formed into monofilamentand multifilament fibers.

The following examples are illustrative of the present invention, butare not to be construed as to limiting its scope in any manner.

EXAMPLE 1 A. Synthesis of p-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

4,4'-Diglycidyloxy-α-methylstilbene (88.68 grams, 0.5 epoxideequivalent) and p-nitrophenol (139.1 grams, 1.0 mole) are added to areactor equipped with a chilled glycol condenser and stirred as a powderunder a nitrogen atmosphere. The 4,4'-diglycidyloxy-α-methylstilbeneused has an epoxide equivalent weight (EEW) of 177.36 and exhibitsmonotropic liquid crystallinity with a 133° C. isotropizationtemperature, 94° C. onset to nematic liquid crystallinity and a 61° C.onset to crystallization. Heating commences and after eleven minutes,90° C. is achieved. At this temperature, ethyltriphenylphosphoniumacetate.acetic acid complex catalyst (70% solids in methanol) (0.2278grams, 0.10% weight of the total reactants) is added to the stirredpowder. Heating continues for five more minutes until 125° C. isachieved and a solution forms. After an additional two minutes ofheating, the temperature reaches 150° C., and heating ceases. After oneminute, exothermic heating to a peak temperature of 171° C. occurs.After an additional nine minutes, the 150° C. temperature is reachievedand is held for the next hour. After this time, the temperature isincreased to 175° C. over a nine minute period and is held therein forthe next 291 minutes. After this time, the reactor is put under a 1 mmHg vacuum while maintaining the 175° C. temperature. After two hours,the vacuum stripped product is recovered as a tacky black solid at 25°C. Epoxide titration of a portion of the product reveals the presence ofno residual epoxide. Fourier transform infrared spectrophotometricanalysis of a potassium bromide pellet of the product reveals thepresence of the expected asymmetric nitro group stretching at 1503 cm⁻¹and the symmetric nitro group stretching at 1337 cm⁻¹ and the hydroxylgroup O--H stretching centered at 3369 cm⁻¹ (broad).

B. Hydrogenation of p-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

A portion (14.56 grams, 0.046 nitro equivalent) of p-nitrophenol adductof 4,4'-diglycidyloxy-α-methylstilbene from A above is dissolved in1,4-dioxane (100 grams) and added to a dropping funnel. Sodiumhydrosulfite (85% technical) (47.11 grams, 0.23 mole active), anhydrouspotassium carbonate (31.78 grams, 0.23 mole) and deionized water (250grams) are added to a reactor and stirred to provide a solution. Aftercooling to 25° C., the 1,4-dioxane solution of the nitro adduct is addeddropwise to the reactor over a 144 minute period and so as to maintainthe 25° C. temperature. The reaction product is maintained for anadditional thirty minutes at 25° C. then stirring is shut off to allowseparation of the aqueous and organic layers to occur. The bottomaqueous layer is pipetted off and discarded, while the top organic layeris rotary evaporated to a dry powder using final conditions of 50° C.and 1 mm Hg. Deionized water (500 milliliters) is added to the drypowder product followed by heating to 70° C. to provide a solution.While still hot, the solution is filtered through Celite then rotaryevaporated to a total volume of 50 milliliters. After cooling to 25° C.,ethanol (200 milliliters) is added to the product with shaking. Theresulting slurry is filtered and the product recovered on the filter isdried in a vacuum oven at 80° C. and 1 mm Hg to a constant weight of12.12 grams of light tan colored powder. Fourier transform infraredspectrophotometric analysis of a potassium bromide pellet of the productreveals the presence of the expected primary amine group N--H stretchingat 3343 and 3283 cm⁻¹ and hydroxyl group O--H stretching at 3442 cm⁻¹,concurrent with complete disappearance of the asymmetric and symmetricnitro group stretching. Titration of a portion of the productdemonstrates the presence of 3.475 milequivalents of --NH₂ per gram ofproduct. This equates to a 287.94 --NH₂ equivalent weight, versus a286.48 theoretical --NH₂ equivalent weight.

EXAMPLE 2 A. Synthesis of m-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

4,4'-Diglycidyloxy-α-methylstilbene (88.68 grams, 0.5 epoxideequivalent) and m-nitrophenol (139.1 grams, 1.0 mole) are added to areactor equipped with a chilled glycol condenser and stirred as a powderunder a nitrogen atmosphere. The 4,4'-diglycidyloxy-α-methylstilbeneused has an epoxide equivalent weight (EEW) of 177.36 and exhibitsmonotropic liquid crystallinity with a 133° C. isotropizationtemperature, 94° C. onset to nematic liquid crystallinity and a 61° C.onset to crystallization. Heating commences and after eleven minutes,90° C. is achieved. At this temperature, ethyltriphenylphosphoniumacetate.acetic acid complex catalyst (70% solids in methanol) (0.2278grams, 0.10% weight of the total reactants) is added to the stirredpowder. Heating continues for seven more minutes until 150° C. isachieved then heating ceases. After two minutes, exothermic heating to apeak temperature of 172° C. occurs. After an additional six minutes, the150° C. temperature is reachieved and is held for the next fifty twominutes. After this time, the temperature is increased to 175° C. over atwelve minute period and is held therein for the next 5 hours. Afterthis time, the reactor is put under a 1 mm Hg vacuum while maintainingthe 175° C. temperature. After two hours, the vacuum stripped product isrecovered as a tacky black solid at 25° C. Epoxide titration of aportion of the product reveals the presence of no residual epoxide.Fourier transform infrared spectrophotometric analysis of a potassiumbromide pellet of the product reveals the presence of the expectedasymmetric nitro group stretching at 1530 cm⁻¹ and the symmetric nitrogroup stretching at 1350 cm⁻¹ and the hydroxyl group O--H stretchingcentered at 3376 cm⁻¹ (broad).

B. Hydrogenation of m-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

A portion (14.56 grams, 0.046 nitro equivalent) of m-nitrophenol adductof 4,4'-diglycidyloxy-α-methylstilbene from A above is dissolved in1,4-dioxane (50 grams) and added to a dropping funnel. Sodiumhydrosulfite (85% technical) (47.11 grams, 0.23 mole active), anhydrouspotassium carbonate (31.78 grams, 0.23 mole) and deionized water (250grams) are added to a reactor and stirred to provide a solution. Aftercooling to 32° C., the 1,4-dioxane solution of the nitro adduct is addeddropwise to the reactor over a one hour period and so as to maintain thereaction temperature between 32° and 36° C. The reaction product ismaintained for an additional two hours while allowing the temperature tocool to 25° C. then stirring is shut off to allow separation of theaqueous and organic layers to occur. The bottom aqueous layer ispipetted off and discarded, while the top organic layer is rotaryevaporated to a dry powder using final conditions of 50° C. and 1 mm Hg.Deionized water (500 milliliters) is added to the dry powder productfollowed by heating to 70° C. to provide a solution. While still hot,the solution is filtered through Celite then rotary evaporated to atotal volume of 50 milliliters. After cooling to 25° C., ethanol (200milliliters) is added to the product with shaking. The resulting slurryis filtered and the product recovered on the filter is dried in a vacuumoven at 80° C. and 1 mm Hg to a constant weight of 9.1 grams of lighttan colored powder. Fourier transform infrared spectrophotometricanalysis of a potassium bromide pellet of the product reveals thepresence of the expected primary amine group N--H stretching andhydroxyl group O--H stretching at 3442 and 3283 (shoulder) cm⁻¹concurrent with complete disappearance of the asymmetric and symmetricnitro group stretching. Titration of a portion of the productdemonstrates the presence of 3.408 milequivalents of --NH₂ per gram ofproduct. This equates to a 293.46 --NH₂ equivalent weight, versus a286.48 theoretical --NH₂ equivalent weight.

EXAMPLE 3 A. Synthesis of 3-Methyl-4-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

4,4'-Diglycidyloxy-α-methylstilbene (88.68 grams, 0.5 epoxideequivalent) and 3-methyl-4-nitrophenol (153.1 grams, 1.0 mole) are addedto a reactor equipped with a chilled glycol condenser and stirred as apowder under a nitrogen atmosphere. The4,4'-diglycidyloxy-α-methylstilbene used has an epoxide equivalentweight (EEW) of 177.36 and exhibits monotropic liquid crystallinity witha 133° C. isotropization temperature, 94° C. onset to nematic liquidcrystallinity and a 61° C. onset to crystallization. Heating commencesand after twelve minutes, 90° C. is achieved. At this temperature,ethyltriphenylphosphonium acetate.acetic acid complex catalyst (70%solids in methanol) (0.2418 grams, 0.10% weight of the total reactants)is added to the stirred powder. Heating continues for nine more minutesuntil 150° C. is achieved and heating of the solution ceases. After fiveminutes, exothermic heating to a peak temperature of 161° C. occurs.After an additional two minutes, the temperature has decreased to 160°C. At this time, the temperature is increased to 175° C. over a sixminute period and is held therein for the next 287 minutes. After thistime, the reactor is put under a 1 mm Hg vacuum while maintaining the175° C. temperature. After two hours, the vacuum stripped product isrecovered as a black solid at 25° C. Epoxide titration of a portion ofthe product reveals the presence of no residual epoxide. Fouriertransform infrared spectrophotometric analysis of a potassium bromidepellet of the product reveals the presence of the expected asymmetricnitro group stretching at 1510 cm⁻¹ (overlaps with aromatic ringabsorption) and the symmetric nitro group stretching at 1337 cm⁻¹ andthe hydroxyl group O--H stretching centered at 3436 cm⁻¹ (broad).

B. Hydrogenation of 3-Methyl-4-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

A portion (15.20 grams, 0.046 nitro equivalent) of3-methyl-4-nitrophenol adduct of 4,4'-diglycidyloxy-α-methylstilbenefrom A above is dissolved in 1,4-dioxane (50 grams) and added to adropping funnel. Sodium hydrosulfite (85% technical) (47.11 grams, 0.23mole active), anhydrous potassium carbonate (31.78 grams, 0.23 mole) anddeionized water (250 grams) are added to a reactor and stirred toprovide a solution. After cooling to 33° C., the 1,4-dioxane solution ofthe nitro adduct is added dropwise to the reactor over a 100 minuteperiod and so as to maintain the reaction temperature between 31° and33° C. The reaction product is maintained for an additional one hourwhile allowing the temperature to cool to 30° C. then stirring is shutoff to allow separation of the aqueous and organic layers to occur. Thebottom aqueous layer is pipetted off and discarded, while the toporganic layer is rotary evaporated to a dry powder using finalconditions of 50° C. and 1 mm Hg. Deionized water (200 milliliters) isadded to the dry powder product followed by heating to 70° C. to providea solution. While still hot, the solution is filtered through Celitethen rotary evaporated to a total volume of 50 milliliters. Aftercooling to 25° C., ethanol (200 milliliters) is added to the productwith shaking. The resulting slurry is filtered and the product recoveredon the filter is dried in a vacuum oven at 80° C. and 1 mm Hg to aconstant weight of 8.10 grams of tan colored powder. Fourier transforminfrared spectrophotometric analysis of a potassium bromide pellet ofthe product reveals the presence of the expected primary amine groupN--H stretching and hydroxyl group O--H stretching at 3429 cm⁻¹ with ashoulder at 3270 cm⁻¹, concurrent with complete disappearance of theasymmetric and symmetric nitro group stretching. Titration of a portionof the product demonstrates the presence of 2.923 milequivalents of--NH₂ per gram of product. This equates to a 342.09 --NH₂ equivalentweight, versus a 300.51 theoretical --NH₂ equivalent weight.

EXAMPLE 4 Copolymerization of p-Aminophenol Adduct of4,4'-Diglycidyoxy-α-metof methylstilbene with4,4'-Diglycidyloxy-α-methylstilbene

A portion (0.1514 gram, 0.00105>NH equivalent) of the p-aminophenoladduct of 4,4'-diglycidyloxy-α-methylstilbene from Example 1-B and4,4'-diglycidyloxy-α-methylstilbene (175.147 epoxide equivalent weight)(0.1842 gram, 0.00105 epoxide equivalent) are added to a ceramic mortarand ground together until a homogeneous powder is formed. A portion(11.9 milligrams) of the adduct and epoxy resin blend is analyzed bydifferential scanning calorimetry using a heating rate of 10° C. perminute under a stream of nitrogen flowing at 35 cubic centimeters perminute and a temperature range from 30° to 300° C. An endotherm isobtained with an onset temperature of 116.2° C., a minimum at 130.4° C.,an endpoint temperature of 138° C. and an enthalpy of 35.4 joules pergram. An exotherm is obtained with an onset temperature of 189.5° C., amaximum at 240.7° C., an endpoint temperature of 268.3° C. and anenthalpy of 121.3 joules per gram. A second exotherm is obtained with anonset temperature of 268.3° C., a maximum at 271.1° C., an endpointtemperature of 292° C. and an enthalpy of 26.7 joules per gram. A secondscanning reveals a 148.5° C. glass transition temperature and anexothermic rise with an onset temperature of 280° C. Analysis of thebrown colored solid product recovered from the differential scanningcalorimetry analysis (second scanning) via crosspolarized lightmicroscopy at 70× magnification reveals a high level of birefringencecaused by dispersed domains having liquid crystalline textures. Analysisof a portion of the adduct and epoxy resin blend via crosspolarizedlight microscopy is completed using a microscope equipped with aprogrammable hot stage using a heating rate of 10° C. per minute and 70×magnification. The following results are obtained:

    ______________________________________                                        Observed                                                                      Transition                                                                    Temperatures (°C.)                                                                      Comments                                                     ______________________________________                                         30              Birefringent solid.                                          126              First melting observed.                                      133              Isotropic melt containing                                                     dispersed crystals of the                                                     adduct.                                                      160              Partial melting of crystals.                                 180              Thermosets, some crystals                                                     still present.                                               230              Begins to darken.                                            260              Birefringent brown solid                                                      containing some crystals.                                    ______________________________________                                    

When cooled to room temperature (24° C.), the product retains itsbirefringent appearance.

Analysis of a second portion of the adduct and epoxy resin blend viacrosspolarized light microscopy is completed using a microscope equippedwith a programmable hot stage preheated to 160° C. and 70×magnification. The blend melts at the 160° C. temperature with thepresence of some crystals. After two minutes, small birefringent domainshaving liquid crystal texture are observed with crystals still present.Upon cooling of this fluid to room temperature (25° C.), the resinsolidifies with retention of the liquid crystal texture.

Analysis of a third portion of the adduct and epoxy resin blend viacrosspolarized light microscopy is completed using a microscope equippedwith a programmable hot stage preheated to 140° C. and 70×magnification. The blend partially melts at the 140° C. temperature withthe presence of some crystals and liquid crystal texture. Shearing ofthe resin at this time, between the glass coverslip and glass microscopeslide produces orientation of the liquid crystalline domains in thedirection perpendicular to that in which the shear is applied.

EXAMPLE 5 Copolymerization of m-Aminophenol Adduct of4,4'-Diglycidyoxy-α-methylstilbene with4,4'-Diglycidyloxy-α-methylstilbene

A portion (0.2001 gram, 0.00136>NH equivalent) of the m-aminophenoladduct of 4,4'-diglycidyloxy-α-methylstilbene from Example 2-B and4,4'-diglycidyloxy-α-methylstilbene (175.147 epoxide equivalent weight)(0.2389 gram, 0.00136 epoxide equivalent) are added to a ceramic mortarand ground together until a homogeneous powder is formed. A portion(23.5 milligrams) of the adduct and epoxy resin blend is analyzed bydifferential scanning calorimetry using a heating rate of 10° C. perminute under a stream of nitrogen flowing at 35 cubic centimeters perminute and a temperature range from 30° to 300° C. An endotherm isobtained with an onset temperature of 116.3° C., a minimum at 128.2° C.,an endpoint temperature of 148° C. and an enthalpy of 37.1 joules pergram. An exotherm is obtained with an onset temperature of 200.7° C., amaximum at 219.8° C., and an endpoint temperature of 258.2° C. A secondexotherm is obtained with an onset temperature of 258.2° C., a maximumat 284.3° C. and an endpoint temperature above 300° C. A second scanningreveals a 137.4° C. glass transition temperature and an exothermic risewith an onset temperature of 280.7° C. Analysis of the brown coloredpowdery (unfused) product recovered from the differential scanningcalorimetry analysis (second scanning) via crosspolarized lightmicroscopy at 70× magnification reveals a high level of birefringence.Analysis of a portion of the adduct and epoxy resin blend viacrosspolarized light microscopy using a microscope equipped with a hotstage using a heating rate of 10° C. per minute and commencing at 30° C.fails to produce meaningful results due to the vaporization of materialfrom the isotropic melt containing crystals once 260° C. is achieved.Analysis of a second portion of the adduct and epoxy resin blend viacrosspolarized light microscopy is completed using a microscope equippedwith a programmable hot stage preheated to 220° or 240° C. In bothcases, the blend immediately solidifies after only partial melting ofthe adduct crystals occurs.

EXAMPLE 6 Preparation of a Casting of the m-Aminophenol Adduct of 4,4'-Diglycidyloxy-α-methylstilbene with 4,4'-Diglycidyloxy-α-methylstilbene

The remaining blend of m-aminophenol adduct of4,4'-diglycidyloxy-α-methylstilbene with4,4'-diglycidyloxy-α-methylstilbene from Example 5 is added to analuminum pan and placed into an oven which has been preheated to 220° C.After one minute at 220° C., the powder has fused together. After anadditional four minutes at 220° C., a brown solid is obtained which ispeeled from the aluminum surface as a film. After a total of 2 hours at220° C., the temperature in the oven is increased to 240° C. After twohours at 240° C., the casting is recovered. Analysis of a portion of thebrown colored casting via crosspolarized light microscopy at 70×magnification reveals a high level of birefringence. A portion (30.0milligrams) of the cured casting of the adduct and epoxy resin blend isanalyzed by differential scanning calorimetry using a heating rate of10° C. per minute under a stream of nitrogen flowing at 35 cubiccentimeters per minute and a temperature range from 30° to 300° C. Noevents are observed up to 262.3° C., at which temperature an exothermicrise begins.

EXAMPLE 7 Copolymerization of 3-Methyl-4-Aminophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene with4,4'-Diglycidyloxy-α-methylstilbene

A portion (0.2040 gram, 0.00119>NH equivalent) of the3-methyl-4-aminophenol adduct of 4,4'-diglycidyloxy-α-methylstilbenefrom Example 3-B and 4,4'-diglycidyloxy-α-methylstilbene (175.147epoxide equivalent weight) (0.2089 gram, 0.00119 epoxide equivalent) areadded to a ceramic mortar and ground together until a homogeneous powderis formed. A portion (12.7 milligrams) of the adduct and epoxy resinblend is analyzed by differential scanning calorimetry using a heatingrate of 10° C. per minute under a stream of nitrogen flowing at 35 cubiccentimeters per minute and a temperature range from 30° to 300° C. Anendotherm is obtained with an onset temperature of 118.9° C., a minimumat 131.8° C., an endpoint temperature of 141° C. and an enthalpy of 40.6joules per gram. An exotherm is obtained with an onset temperature of222.6° C., a maximum at 236.4° C., an endpoint temperature of 281.9° C.,and an enthalpy of 137.5 joules per gram. A second exotherm is obtainedwith an onset temperature of 281.9° C., a maximum at 291.3 and anendpoint temperature above 300° C. A second scanning reveals a 140.7° C.glass transition temperature and an exothermic rise with an onsettemperature of 272.3° C.

EXAMPLE 8 Preparation of a Casting of the 3-Methyl-4-Aminophenol Adductof 4,4'-Diglycidyloxy-α-methylstilbene with4,4'-Diglycidyloxy-α-methylstilbene

The remaining blend of 3-methyl-4-aminophenol adduct of4,4'-diglycidyloxy-α-methylstilbene with4,4'-diglycidyloxy-α-methylstilbene from Example 7 is added to analuminum pan and placed into an oven which has been preheated to 210° C.After two minutes at 210° C., softening is observed. After an additionalthree minutes at 210° C., solidification occurs. After a total of 2hours at 210° C., the temperature in the oven is increased to 230° C.After two hours at 230° C., the casting is recovered. Analysis of aportion of the brown colored casting via crosspolarized light microscopyat 70× magnification reveals a high level of birefringence. A portion(40.0 milligrams) of the casting of the adduct and epoxy resin blend isanalyzed by differential scanning calorimetry using a heating rate of10° C. per minute under a stream of nitrogen flowing at 35 cubiccentimeters per minute and a temperature range from 30° to 300° C. Noevents are observed up to 249.7° C., at which temperature an exothermicrise begins. A second scanning reveals no events up to 260.4° C., atwhich temperature an exothermic rise begins.

EXAMPLE 9 A. Synthesis of p-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

4,4'-Diglycidyloxy-α-methylstilbene (53.21 grams, 0.30 epoxideequivalent) and p-nitrophenol (42.15 grams, 0,303 mole) are added to areactor equipped with a chilled glycol condenser and stirred as a powderunder a nitrogen atmosphere. The 4,4'-diglycidyloxy-α-methylstilbeneused has an epoxide equivalent weight (EEW) of 177.36 and exhibitsmonotropic liquid crystallinity with a 133° C. isotropizationtemperature, 94° C. onset to nematic liquid crystallinity and a 61° C.onset to crystallization. Heating commences and after eight minutes, 90°C. is achieved. At this temperature, ethyltriphenylphosphoniumacetate.acetic acid complex catalyst (70% solids in methanol) (0.0954grams, 0.10% weight of the total reactants) is added to the stirredpowder. Heating continues for seven more minutes until 125° C. isachieved and a solution forms. After an additional two minutes ofheating, the temperature reaches 150° C., heating ceases and air coolingof the reactor exterior is employed. An exotherm to 170° C. occurs twominutes later with cooling to 150° C. after an additional four minutes,at which time air cooling of the reactor ceases. After an additional sixhours at the 150° C. temperature, the product is recovered as a brittleblack solid at 25° C. Epoxide titration of a portion of the productreveals the presence of no residual epoxide. Fourier transform infraredspectrophotometric analysis of a neat film of the product on a potassiumchloride plate reveals the presence of the expected asymmetric nitrogroup stretching at 1497 cm⁻¹ and the symmetric nitro group stretchingat 1337 cm⁻¹ and the hydroxyl group O--H stretching centered at 3462cm⁻¹ (broad).

B. Methylation of the p-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

A portion (15.86 grams, 0.05 hydroxyl equivalent) of p-nitrophenoladduct of 4,4'-diglycidyloxy-α-methylstilbene from A above and acetone(100 milliliters) are added to a reactor and stirred under a nitrogenatmosphere to provide a solution. Sodium hydroxide (97%) (12.0 grams,0.30 mole) dissolved in deionized water (18.0 grams) is added to adropping funnel. Dimethyl sulfate (18.92 grams, 0.15 mole) is added to aseparate dropping funnel. While at room temperature (23° C.), a portion(7.5 milliliters) of the aqueous sodium hydroxide solution is added tothe reactor followed by heating to 50° C. Once the 50° C. temperature isachieved, the remaining aqueous sodium hydroxide and dimethyl sulfateare added simultaneously and dropwise to the reactor over a 118 minuteperiod while maintaining the reaction temperature at 50° C. The reactionproduct is maintained for an additional 45 minutes at 50° C. The productis rotary evaporated to a dry powder using final conditions of 80° C.and 1 mm Hg. Deionized water (250 milliliters) and methylene chloride(250 milliliters) are added to the dry powder product to provide asolution. The methylene chloride layer is separated using a separatoryfunnel, then washed with two portions (100 milliliters) of deionizedwater. The methylene chloride layer is dried over anhydrous sodiumsulfate then filtered. Rotary evaporation of the methylene chloride iscompleted using final conditions of 105° C. and 1 mm Hg to provide aconstant weight of 16.29 grams of black brittle solid at 25° C. Fouriertransform infrared spectrophotometric analysis of a neat film of theproduct on a potassium chloride plate reveals the complete disappearanceof the hydroxyl group O--H stretching, the presence of the expectedasymmetric nitro group stretching at 1497 cm⁻¹ and the symmetric nitrogroup stretching at 1344 cm⁻¹ and the appearance of methoxy group --C--Hstretching at 2837 cm⁻¹.

C. Hydrogenation of Methylated p-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

A portion (16.27 grams, 0.0491 nitro equivalent) of methylatedp-nitrophenol adduct of 4,4'-diglycidyloxy-α-methylstilbene from B aboveis dissolved in 1,4-dioxane (80 grams) and then added to a droppingfunnel. Sodium hydrosulfite (85% technical) (50.30 grams, 0.2456 moleactive), anhydrous potassium carbonate (33.94 grams, 0.2456 mole),deionized water (250 grams) and 1,4-dioxane (150 grams) are added to areactor and stirred to provide a solution. After cooling to 32° C., the1,4-dioxane solution of the nitro adduct is added dropwise to thereactor over a thirty minute period and so as to maintain the reactiontemperature between 28° and 32° C. The reaction product is maintainedfor an additional fifteen hours while allowing the temperature to coolto 25° C. then stirring is shut off to allow separation of the aqueousand organic layers to occur. The bottom aqueous layer is pipetted offand discarded, while the top organic layer is rotary evaporated to a drypowder using final conditions of 120° C. and 1 mm Hg. Methylene chloride(300 milliliters) is added to the dry powder product followed by mixingto provide a slurry. The slurry is filtered through a coarse frittedglass funnel then recovered and added to 60° C. deionized water (300milliliters) with stirring. Once a stirred solution is obtained,isopropanol (1200 milliliters) is added in 300 milliliter portions tothe stirred solution. After stirring the resulting slurry for thirtyminutes, filtration through a medium fritted glass funnel is completedand the product recovered on the filter is washed with isopropanol (100milliliters), then dried in a vacuum oven at 80° C. and 1 mm Hg to aconstant weight of 11.02 grams of light tan colored powder. Fouriertransform infrared spectrophotometric analysis of a potassium bromidepellet of the product reveals the presence of the expected primary aminegroup N--H stretching 3442 and 3263 (shoulder) cm⁻¹, concurrent withcomplete disappearance of the asymmetric and symmetric nitro groupstretching and the methoxy group --C--H stretching at 2831 cm⁻¹.Titration of a portion of the product demonstrates the presence of 3.316milequivalents of --NH₂ per gram of product. This equates to a 301.57--NH₂ equivalent weight, versus a 300.51 theoretical --NH₂ equivalentweight.

D. Analysis of the Methylated p-Aminophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene for Liquid Crystallinity

A portion (23.5 milligrams) of the adduct from C above is analyzed bydifferential scanning calorimetry using a heating rate of 10° C. perminute under a stream of nitrogen flowing at 35 cubic centimeters perminute and a temperature range from 30° to 300° C. An endotherm isobtained with an onset temperature of 54.8° C., a minimum at 139.8° C.,an endpoint temperature of 182.5° C. and an enthalpy of 123.1 joules pergram. Analysis of the brown colored powdery (unfused) product recoveredfrom the differential scanning calorimetry analysis via crosspolarizedlight microscopy at 70× magnification reveals a high level ofbirefringence. Analysis of a portion of the methylated adduct viacrosspolarized light microscopy is completed using a microscope equippedwith a programmable hot stage using a heating rate of 10° C. per minuteand 70× magnification. The following results are obtained:

    ______________________________________                                        Observed                                                                      Transition                                                                    Temperatures (°C.)                                                                     Comments                                                      ______________________________________                                         30             Opaque powder.                                                125             First softening observed.                                     183             Partial melt, birefringent.                                   195             Fuses to birefringent solid.                                  220             Semi-solid, birefringent.                                     234             Partial melt, birefringent.                                   245             Viscous, birefringent melt                                                    with liquid crystal texture                                                   present.                                                      300             Same as at 245° C., darkens to                                         reddish brown color.                                          ______________________________________                                    

When cooled to room temperature (24° C.), the product retains itsbirefringent appearance.

EXAMPLE 10

Copolymerization of Methylated p-Aminophenol Adduct of4,4'-Diglycidyoxy-α-methylstilbene with4,4'-Diglycidyloxy-α-methylstilbene Using 1:1 --NH to EpoxideStoichiometry

A portion (0.2959 gram, 0.00196>NH equivalent) of the methylatedp-aminophenol adduct of 4,4'-diglycidyloxy-α-methylstilbene from Example9-C and 4,4'-diglycidyloxy-α-methylstilbene (177.355 epoxide equivalentweight) (0.3480 gram, 0.00196 epoxide equivalent) are added to a ceramicmortar and ground together until a homogeneous powder is formed. Aportion (16.6 milligrams) of the adduct and epoxy resin blend isanalyzed by differential scanning calorimetry using a heating rate of10° C. per minute under a stream of nitrogen flowing at 35 cubiccentimeters per minute and a temperature range from 30° to 300° C. Anendotherm is obtained with an onset temperature of 118.4° C., a minimumat 129.7° C., an endpoint temperature of 140° C. and an enthalpy of 33.9joules per gram. An exotherm is obtained with an onset temperature of184.4° C., a maximum at 194.7° C., an endpoint temperature of 220.5° C.and an enthalpy of 174.6 joules per gram. A second scanning reveals a108.4° C. glass transition temperature and an exothermic rise with anonset temperature of 267.7° C. Analysis of the fused, opaque, darkreddish brown colored solid product recovered from the differentialscanning calorimetry analysis (second scanning) via crosspolarized lightmicroscopy at 70× magnification revealed a high level of birefringence.Analysis of a portion of the methylated adduct and epoxy resin blend viacrosspolarized light microscopy is completed using a microscope equippedwith a programmable hot stage using a heating rate of 10° C. per minuteand 70× magnification. The following results are obtained:

    ______________________________________                                        Observed                                                                      Transition                                                                    Temperatures (°C.)                                                                      Comments                                                     ______________________________________                                         30              Opaque solid.                                                126              Partial melting observed.                                    134              Viscous melt containing                                                       large birefringent regions                                                    possessing liquid crystal                                                     texture.                                                     150              Semi-solid containing large                                                   birefringent regions.                                        170              Application of shear                                                          produces birefringent                                                         striations in the shear                                                       direction.                                                   191              Birefringent phase is                                                         starting to clear.                                           200              Resin has solidified                                                          maintaining low level of                                                      birefringence.                                               218              Schlieren type textures                                                       developing.                                                  250              High level of birefringence                                                   and Schlieren texture                                                         present in the solid.                                        ______________________________________                                    

When cooled to room temperature (24° C.), the product retains itsbirefringence and Schlieren textures.

EXAMPLE 11

Preparation of a Casting of the Methylated p-Aminophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene with4,4'-Diglycidyloxy-α-methylstilbene

The remaining blend of methylated p-aminophenol adduct of4,4'-diglycidyloxy-α-methylstilbene with4,4'-diglycidyloxy-α-methylstilbene from Example 10 is added to analuminum pan and placed into an oven which has been preheated to 180° C.Within five minutes at 180° C., the powder melt flows to a rubberysolid. After a total of 1 hour at 180° C., the temperature in the ovenis increased to 200° C. After one hour at 200° C., the temperature inthe oven is increased to 230° C. After two hours at 230° C., the castingis recovered. Analysis of a portion of the semi-translucent, reddishbrown colored casting via crosspolarized light microscopy at 70×magnification reveals a high level of birefringence. A portion (40.0milligrams) of the cured casting of the adduct and epoxy resin blend isanalyzed by differential scanning calorimetry using a heating rate of10° C. per minute under a stream of nitrogen flowing at 35 cubiccentimeters per minute and a temperature range from 30° to 300° C. Aglass transition temperature of 150.7° C. is observed with an exothermicrise with an onset temperature of 263.6° C. A second scanning reveals a150.6° C. glass transition temperature and an exothermic rise with anonset temperature of 270.1° C.

EXAMPLE 12 Copolymerization of Methylated p-Aminophenol Adduct of4,4'-Diglycidyoxy-α-methylstilbene with4,4'-Diglycidyloxy-α-methylstilbene Using 2:1 --NH to EpoxideStoichiometry

A portion (0.2407 gram, 0.001596>NH equivalent) of the methylatedp-aminophenol adduct of 4,4'-diglycidyloxy-α-methylstilbene from Example9-C and 4,4'-diglycidyloxy-α-methylstilbene (177.355 epoxide equivalentweight) (0.1415 gram, 0.000798 epoxide equivalent) are added to aceramic mortar and ground together until a homogeneous powder is formed.A portion (13.5 milligrams) of the adduct and epoxy resin blend isanalyzed by differential scanning calorimetry using a heating rate of10° C. per minute under a stream of nitrogen flowing at 35 cubiccentimeters per minute and a temperature range from 30° to 300° C. Anendotherm is obtained with an onset temperature of 116.3° C., a minimumat 129.1° C., an endpoint temperature of 136.8° C. and an enthalpy of17.5 joules per gram. An exotherm is obtained with an onset temperatureof 205.0° C., a maximum at 215.9° C., an endpoint temperature of 224.8°C. and an enthalpy of 125.7 joules per gram. A second exotherm isobtained with an onset temperature of 230.3° C., a maximum at 234.4° C.,an endpoint temperature of 244.4° C. and an enthalpy of 11.0 joules pergram. A second scanning reveals a 116.1° C. glass transition temperatureand an exothermic rise with an onset temperature of 265.4° C. Analysisof the fused, opaque, brown colored solid product recovered from thedifferential scanning calorimetry analysis (second scanning) viacrosspolarized light microscopy at 70× magnification reveals a highlevel of birefringence. Analysis of a portion of the methylated adductand epoxy resin blend via crosspolarized light microscopy is completedusing a microscope equipped with a programmable hot stage using aheating rate of 10° C. per minute and 70× magnification. The followingresults are obtained:

    ______________________________________                                        Observed                                                                      Transition                                                                    Temperatures (°C.)                                                                      Comments                                                     ______________________________________                                         30              Opaque solid.                                                128              Melting observed.                                            140              Semi-solid containing large                                                   birefringent regions                                                          possessing liquid crystal                                                     texture.                                                     170              Application of shear                                                          produces birefringent                                                         striations in the shear                                                       direction.                                                   184              Resin has solidified with                                                     slight reduction in                                                           birefringence.                                               250              Same as at 184° C.                                    ______________________________________                                    

When cooled to room temperature (24° C.), the product exhibits a highlevel of birefringence with some Schlieren textures.

EXAMPLE 13

Preparation of a Casting of the Methylated p-Aminophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene with4,4'-Diglycidyloxy-α-methylstilbene

The remaining blend of methylated p-aminophenol adduct of4,4'-diglycidyloxy-α-methylstilbene with4,4'-diglycidyloxy-α-methylstilbene from Example 12 is added to analuminum pan and placed into an oven which has been preheated to 180° C.Within two minutes at 180° C., the powder melt flows to an opaque solid.After a total of 1 hour at 180° C., the temperature in the oven isincreased to 200° C. After one hour at 200° C., the temperature in theoven is increased to 230° C. After two hours at 230° C., the casting isrecovered. Analysis of a portion of the opaque, reddish brown, coloredcasting via crosspolarized light microscopy at 70× magnification revealsa high level of birefringence. A portion (40.0 milligrams) of the curedcasting of the adduct and epoxy resin blend is analyzed by differentialscanning calorimetry using a heating rate of 10° C. per minute under astream of nitrogen flowing at 35 cubic centimeters per minute and atemperature range from 30° to 300° C. No events are observed up to254.1° C., at which temperature an exothermic rise begins. A secondscanning reveals an increase in the onset temperature of the exothermicrise to 274.0° C.

EXAMPLE 14 A. Synthesis of o-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

4,4'-Diglycidyloxy-α-methylstilbene (88.68 grams, 0.5 epoxideequivalent) and o-nitrophenol (70.25 grams, 0.505 mole) are added to areactor equipped with a chilled glycol condenser and stirred as a powderunder a nitrogen atmosphere. The 4,4'-diglycidyloxy-α-methylstilbeneused has an epoxide equivalent weight (EEW) of 177.36 and exhibitsmonotropic liquid crystallinity with a 133° C. isotropizationtemperature, 94° C. onset to nematic liquid crystallinity and a 61° C.onset to crystallization. Heating commences and after nine minutes, 90°C. is achieved. At this temperature, ethyltriphenylphosphoniumacetate.acetic acid complex catalyst (70% solids in methanol) (0.159grams, 0.10% weight of the total reactants) is added to the stirredpowder. Heating continues for eight more minutes until 150° C. isachieved then heating ceases. After three minutes, exothermic heating toa peak temperature of 187° C. occurs. After an additional seventeenminutes, the 150° C. temperature is reachieved and is held for the nexteight hours. After this time, the product is recovered as an amber,transparent solid at 25° C. Epoxide titration of a portion of theproduct reveals the presence of no residual epoxide. Fourier transforminfrared spectrophotometric analysis of a film of the product on apotassium chloride plate reveals the presence of the expected asymmetricnitro group stretching at 1530 cm⁻¹ and the symmetric nitro groupstretching at 1350 cm⁻¹ and the hydroxyl group O--H stretching centeredat 3475 cm⁻¹ (broad).

B. Hydrogenation of o-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

A portion (14.56 grams, 0,046 nitro equivalent) of o-nitrophenol adductof 4,4'-diglycidyloxy-α-methylstilbene from A above is dissolved in1,4-dioxane (50 grams) and added to a dropping funnel. Sodiumhydrosulfite (85% technical) (47.11 grams, 0.23 mole active), anhydrouspotassium carbonate (31.78 grams, 0.23 mole) and deionized water (250grams) are added to a reactor and stirred to provide a solution. Aftercooling to 32° C., the 1,4-dioxane solution of the nitro adduct is addeddropwise to the reactor over a one hour period and so as to maintain thereaction temperature between 32° and 38° C. The reaction product ismaintained for an additional three hours while allowing the temperatureto cool to 27° C. then stirring is shut off to allow separation of theaqueous and organic layers to occur. The bottom aqueous layer ispipetted off and discarded, while the top organic layer is rotaryevaporated to a dry powder using final conditions of 50° C. and 1 mm Hg.Deionized water (200 milliliters) is added to the dry powder productfollowed by heating to 70° C. to provide a solution. While still hot,the solution is filtered through Celite then rotary evaporated to atotal volume of 50 milliliters. After cooling to 24° C., ethanol (200milliliters) is added to the product with shaking. The resulting slurryis filtered and the product recovered on the filter is dried in a vacuumoven at 80° C. and 1 mm Hg to a constant weight of 7.55 grams of lighttan colored powder. Fourier transform infrared spectrophotometricanalysis of a potassium bromide pellet of the product reveals thepresence of the expected primary amine group N--H stretching andhydroxyl group O--H stretching at 3442 cm⁻¹, concurrent with completedisappearance of the asymmetric and symmetric nitro group stretching.Titration of a portion of the product demonstrates the presence of 3,616milequivalents of --NH₂ per gram of product. This equates to a 276.55--NH₂ equivalent weight, versus a 286.48 theoretical --NH₂ equivalentweight.

EXAMPLE 15 Copolymerization of o-Aminophenol Adduct of4,4'-Diglycidyoxy-α-methylstilbene with4,4'-Diglycidyloxy-α-methylstilbene

A portion (0.2894 gram, 0.00209>NH equivalent) of the o-aminophenoladduct of 4,4'-diglycidyloxy-α-methylstilbene from Example 10-B and4,4'-diglycidyloxy-α-methylstilbene (177,355 epoxide equivalent weight)(0.3712 gram, 0.00209 epoxide equivalent) are added to a ceramic mortarand ground together until a homogeneous powder is formed. A portion(20.6 milligrams) of the adduct and epoxy resin blend is analyzed bydifferential scanning calorimetry using a heating rate of 10° C. perminute under a stream of nitrogen flowing at 35 cubic centimeters perminute and a temperature range from 30° to 300° C. An endotherm isobtained with an onset temperature of 125.2° C., a minimum at 135.6° C.,an endpoint temperature of 141° C. and an enthalpy of 39.9 joules pergram. An exotherm is obtained with an onset temperature of 142.9° C., amaximum at 163.2° C., and an endpoint temperature of 204° C. A secondexotherm is obtained with an onset temperature of 232.3° C., a maximumat 266.3, an endpoint temperature at 289° C. and an enthalpy of 61.4joules per gram. A second scanning reveals no events up to 267.6° C., atwhich temperature an exothermic rise begins. Analysis of the opaquesolid (fused) product from the differential scanning analysis viacrosspolarized light microscopy at 70× magnification reveals a highlevel of birefringence.

EXAMPLE 16 A. Ethylation of the p-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

A portion (15.86 grams, 0.05 hydroxyl equivalent) of p-nitrophenoladduct of 4,4'-diglycidyloxy-α-methylstilbene from Example 9-A andacetone (100 milliliters) are added to a reactor and stirred under anitrogen atmosphere to provide a solution. Sodium hydroxide (97%) (12.0grams, 0.30 mole) dissolved in deionized water (18.0 grams) is added toa dropping funnel. Diethyl sulfate (23.13 grams, 0.15 mole) is added toa separate dropping funnel. While at room temperature (23° C.), aportion (7.5 milliliters) of the aqueous sodium hydroxide solution isadded to the reactor followed by heating to 50° C. Once the 50° C.temperature is achieved, the remaining aqueous sodium hydroxide anddiethyl sulfate are added simultaneously and dropwise to the reactorover a 15 minute period while maintaining the reaction temperature at50° C. The reaction product is maintained for an additional 219 minutesat 50° C. The product is rotary evaporated to a dry powder using finalconditions of 80° C. and 1 mm Hg. Deionized water (250 milliliters) andmethylene chloride (250 milliliters) are added to the dry powder productto provide a solution. The methylene chloride layer is separated using aseparatory funnel, then washed with two portions (100 milliliters) ofdeionized water. The methylene chloride layer is dried over anhydroussodium sulfate then filtered. Rotary evaporation of the methylenechloride is completed using final conditions of 105° C. and 1 mm Hg toprovide a constant weight of 16.89 grams of black brittle solid at 25°C. Fourier transform infrared spectrophotometric analysis of a neat filmof the product on a potassium chloride plate reveals the completedisappearance of the hydroxyl group O--H stretching, the presence of theexpected asymmetric nitro group stretching at 1497 cm⁻¹ and thesymmetric nitro group stretching at 1344 cm⁻¹ and the appearance of--CH₃ group symmetric --C--H bending at 1390 cm⁻¹ and primary ethergroup --C--O stretching at 1111 cm⁻¹.

B. Hydrogenation of Ethylated p-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

A portion (16.87 grams, 0.0489 nitro equivalent) of ethylatedp-nitrophenol adduct of 4,4'-diglycidyloxy-α-methylstilbene from A aboveis dissolved in 1,4-dioxane (80 grams) and then added to a droppingfunnel. Sodium hydrosulfite (85% technical) (50.04 grams, 0.2443 moleactive), anhydrous potassium carbonate (33.76 grams, 0.2443 mole),deionized water (250 grams) and 1,4-dioxane (150 grams) are added to areactor and stirred to provide a solution. After cooling to 32° C., the1,4-dioxane solution of the nitro adduct is added dropwise to thereactor over a twenty-five minute period and so as to maintain thereaction temperature at 32° C. The reaction product is maintained for anadditional fifteen hours while allowing the temperature to cool to 22°C. then stirring is shut off to allow separation of the aqueous andorganic layers to occur. The bottom aqueous layer is pipetted off anddiscarded, while the top organic layer is rotary evaporated to a drypowder using final conditions of 120 ° C. and 1 mm Hg. Methylenechloride (150 milliliters) is added to the dry powder product followedby mixing to provide a slurry. The slurry is filtered through a coarsefritted glass funnel then recovered and added to 75° C. deionized water(250 milliliters) with stirring. Once a stirred solution is obtained,isopropanol (1200 milliliters) is added in 300 milliliter portions tothe stirred solution. After stirring the resulting slurry for thirtyminutes, filtration through a medium fritted glass funnel is completedand the product recovered on the filter is washed with isopropanol (100milliliters), then dried in a vacuum oven at 80° C. and 1 mm Hg to aconstant weight of 10.9 grams of light tan colored powder. Fouriertransform infrared spectrophotometric analysis of a neat film of theproduct on a potassium chloride plate reveals the presence of theexpected primary amine group N--H stretching 3449 and 3256 (shoulder)cm⁻¹ concurrent with complete disappearance of the asymmetric andsymmetric nitro group stretching, the --CH₃ group symmetric --C--Hbending at 1384 cm⁻¹ and primary ether group --C--O stretching at 1111cm⁻¹. Titration of a portion of the product demonstrates the presence of3,075 milequivalents of --NH₂ per gram of product. This equates to a325.20 --NH₂ equivalent weight, versus a 314.52 theoretical --NH₂equivalent weight.

C. Analysis of the Ethylated p-Aminophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene for Liquid Crystallinity

A portion (28.5 milligrams) of the adduct from C above is analyzed bydifferential scanning calorimetry using a heating rate of 10° C. perminute under a stream of nitrogen flowing at 35 cubic centimeters perminute and a temperature range from 30° to 300° C. An exotherm isobtained with an onset temperature of 280.6° C., a maximum at 287.6° C.,and an endpoint temperature>300° C. Analysis of a portion of theethylated adduct via crosspolarized light microscopy is completed usinga microscope equipped with a programmable hot stage using a heating rateof 10° C. per minute and 70× magnification. The following results areobtained:

    ______________________________________                                        Observed                                                                      Transition                                                                    Temperatures (°C.)                                                                      Comments                                                     ______________________________________                                         30              Birefringent, opaque powder.                                 110              First softening observed                                     180              Partial melt, birefringent.                                  200              Semi-solid, birefringent.                                    245              Partial isotropic, dispersed                                                  crystals present.                                            277              Viscous, translucent (non-                                                    birefringent) melt with                                                       dispersed crystals present.                                  280              Same as at 277° C., but less                                           dispersed crystals present,                                                   begins to darken.                                            ______________________________________                                    

When cooled to room temperature (24° C.), the product issemi-translucent with dispersed crystals and regions which exhibitbirefringence.

EXAMPLE 17 Copolymerization of Ethylated p-Aminophenol Adduct of4,4'-Diglycidyoxy-α-methylstilbene with4,4'-Diglycidyloxy-α-methylstilbene Using 1:1 --NH to EpoxideStoichiometry

A portion (0.3263 gram, 0.00201>NH equivalent) of the ethylatedp-aminophenol adduct of 4,4'-diglycidyloxy-α-methylstilbene from Example16-B and 4,4'-diglycidyloxy-α-methylstilbene (177.355 epoxide equivalentweight) (0.3559 gram, 0.00201 epoxide equivalent) are added to a ceramicmortar and ground together until a homogeneous powder is formed. Aportion (17.7 milligrams) of the adduct and epoxy resin blend isanalyzed by differential scanning calorimetry using a heating rate of10° C. per minute under a stream of nitrogen flowing at 35 cubiccentimeters per minute and a temperature range from 30° to 300° C. Anendotherm is obtained with an onset temperature of 120.6° C., a minimumat 132.5° C., an endpoint temperature of 145.7° C. and an enthalpy of40.6 joules per gram. An exotherm is obtained with an onset temperatureof 185.6° C., a maximum at 202.1° C., an endpoint temperature of 222.8°C. and an enthalpy of 97.3 joules per gram. A second scanning reveals a124.0° C. glass transition temperature and an exothermic rise with anonset temperature of 203.8° C. Analysis of the fused, opaque, darkreddish black colored solid product recovered from the differentialscanning calorimetry analysis (second scanning) via crosspolarized lightmicroscopy at 70× magnification revealed a high level of birefringencewith liquid crystal textures present. Analysis of a portion of theethylated adduct and epoxy resin blend via crosspolarized lightmicroscopy is completed using a microscope equipped with a programmablehot stage using a heating rate of 10° C. per minute and 70×magnification. The following results are obtained:

    ______________________________________                                        Observed                                                                      Transition                                                                    Temperatures (°C.)                                                                      Comments                                                     ______________________________________                                         30              Birefringent solid.                                           95              Partial softening observed.                                  121              Melting observed.                                            132              Partial melt (non-                                                            birefringent) plus                                                            agglomerated birefringent                                                     regions.                                                     220              Some clearing of                                                              agglomerated birefringent                                                     regions observed.                                            230              Resin is starting to                                                          solidify, birefringent                                                        textures and agglomerated                                                     birefringent regions are                                                      present.                                                     240              Resin has thermoset,                                                          birefringent agglomerated                                                     regions have cleared,                                                         material has darkened.                                       ______________________________________                                    

When cooled to room temperature (24° C.), the brown colored product ishighly birefringent. Analysis of a second portion of the adduct andepoxy resin blend via crosspolarized light microscopy is completed usinga microscope equipped with a programmable hot stage preheated to 180° C.A partial melt is achieved within 20 seconds followed by mixing of theresin by moving the coverslip on the glass microscope slide. After 2.5minutes a semi-solid with birefringent textures is observed. After 6minutes, the resin appears unchanged. Upon cooling to room temperature(24° C.), an opaque, light brown colored solid is obtained whichexhibits a high level of birefringence.

EXAMPLE 18 Copolymerization of Ethylated p-Aminophenol Adduct of4,4'-Diglycidyoxy-α-methylstilbene with4,4'-Diglycidyloxy-α-methylstilbene Using 2:1 --NH to EpoxideStoichiometry

A portion (0.3072 gram, 0.001889>NH equivalent) of the methylatedp-aminophenol adduct of 4,4'-diglycidyloxy-α-methylstilbene from Example16-B and 4,4'-diglycidyloxy-α-methylstilbene (77,355 epoxide equivalentweight) (0.1675 gram, 0.000944 epoxide equivalent) are added to aceramic mortar and ground together until a homogeneous powder is formed.A portion (20.8 milligrams) of the adduct and epoxy resin blend isanalyzed by differential scanning calorimetry using a heating rate of10° C. per minute under a stream of nitrogen flowing at 35 cubiccentimeters per minute and a temperature range from 30° to 250° C. Anendotherm is obtained with an onset temperature of 19.9° C., a minimumat 130.3° C., an endpoint temperature of 139.5° C. and an enthalpy of21.6 joules per gram. An exotherm is obtained with an onset temperatureof 187.5° C., a maximum at 200.6° C., an endpoint temperature of 217.9°C. and an enthalpy of 122.6 joules per gram. A second scanning reveals a120.7° C. glass transition temperature and an exothermic rise with anonset temperature of 241.7° C. Analysis of the fused, opaque, darkreddish black colored solid product recovered from the differentialscanning calorimetry analysis (second scanning) via crosspolarized lightmicroscopy at 70× magnification reveals a high level of birefringencewith liquid crystal textures present. Analysis of a portion of theethylated adduct and epoxy resin blend via crosspolarized lightmicroscopy is completed using a microscope equipped with a programmablehot stage using a heating rate of 10° C. per minute and 70×magnification. The following results are obtained:

    ______________________________________                                        Observed                                                                      Transition                                                                    Temperatures (°C.)                                                                      Comments                                                     ______________________________________                                         30              Birefringent solid.                                          115              Partial softening observed.                                  122              Partial melting observed.                                    132              Partial melt (non-                                                            birefringent) plus                                                            agglomerated birefringent                                                     regions.                                                     200              Resin is semi-solid with                                                      some clearing of                                                              agglomerated birefringent                                                     regions.                                                     240              Resin has thermoset,                                                          birefringent agglomerated                                                     regions have cleared.                                        ______________________________________                                    

When cooled to room temperature (24° C.), the brown colored,semi-translucent product is birefringent. Analysis of a second portionof the adduct and epoxy resin blend via crosspolarized light microscopyis completed using a microscope equipped with a programmable hot stagepreheated to 185° C. A partial melt is achieved within 30 secondsfollowed by mixing of the resin by moving the coverslip on the glassmicroscope slide. After 2 minutes a semi-solid with birefringenttextures is observed. After 6 minutes, the resin appears unchanged. Uponcooling to room temperature (24° C.), a semi-translucent, light browncolored solid is obtained which exhibits birefringent textures.

EXAMPLE 19 A. Synthesis of o-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

4,4'-Diglycidyloxy-α-methylstilbene (53.51 grams, 0.30 epoxideequivalent) and o-nitrophenol (42.15 grams, 0.303 mole) are added to areactor equipped with a chilled glycol condenser and stirred as a powderunder a nitrogen atmosphere. The 4,4'-diglycidyloxyα-methylstilbene usedhas an epoxide equivalent weight (EEW) of 178.36 and exhibits monotropicliquid crystallinity with a 129.9° C. isotropization temperature, 92.9°C. onset to nematic liquid crystallinity and a 67° C. onset tocrystallization. Heating commences until 140° C. is reached withformation of a solution. After cooling to 100° C.,ethyltriphenylphosphonium acetate.acetic acid complex catalyst (70%solids in methanol) (0,096 grams, 0.10% weight of the total reactants)dissolved in methylene chloride (6 milliliters) is added to the stirredpowder. Heating continues for ten minutes until 50° C. is achieved thenheating ceases. After 263 minutes at the 150° C. temperature the productis recovered as a light amber, transparent solid at 25° C. Epoxidetitration of a portion of the product reveals the presence of noresidual epoxide. Fourier transform infrared spectrophotometric analysisof a film of the product on a potassium chloride plate reveals thepresence of the expected asymmetric nitro group stretching at 1523 cm⁻¹and the symmetric nitro group stretching at 1350 cm⁻¹ and the hydroxylgroup O--H stretching centered at 3473 cm⁻¹ (broad).

B. Methylation of the o-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

A portion (31.73 grams, 0.10 hydroxyl equivalent) of o-nitrophenoladduct of 4,4'-diglycidyloxy-α-methylstilbene from A above and acetone(200 milliliters) are added to a reactor and stirred under a nitrogenatmosphere to provide a solution. Sodium hydroxide (97%) (24.0 grams,0.60 mole) dissolved in deionized water (36.0 grams) is added to adropping funnel. Dimethyl sulfate (37.84 grams, 0.30 mole) is added to aseparate dropping funnel. While at room temperature (21° C.), a portion(15 milliliters) of the aqueous sodium hydroxide solution is added tothe reactor followed by heating to 52° C. Once the 52° C. temperature isachieved, the remaining aqueous sodium hydroxide and dimethyl sulfateare added simultaneously and dropwise to the reactor over a five minuteperiod while maintaining the reaction temperature at 52° C. The reactionproduct is maintained for an additional 3 hours at 50°-52° C. Theproduct is rotary evaporated to a dry powder using final conditions of100° C. and 1 mm Hg. Deionized water (250 milliliters) and methylenechloride (250 milliliters) are added to the dry powder product toprovide a solution. The methylene chloride layer is separated using aseparatory funnel. A second portion (250 milliliters) of methylenechloride is used to extract the water layer, then separated using aseparatory funnel. The combined methylene chloride extracts are driedover anhydrous sodium sulfate then filtered. Rotary evaporation of themethylene chloride is completed using final conditions of 105° C. and 1mm Hg to provide a constant weight of 32.3 grams of black brittle solidat 25° C. Fourier transform infrared spectrophotometric analysis of aneat film of the product on a potassium chloride plate reveals thecomplete disappearance of the hydroxyl group O--H stretching, thepresence of the expected asymmetric nitro group stretching at 1497 cm⁻¹and the symmetric nitro group stretching at 1350 cm⁻¹ and the appearanceof methoxy group --C--H stretching at 2831 cm⁻¹.

C. Hydrogenation of Methylated o-Nitrophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene

A portion (32.2 grams, 0.0972 nitro equivalent) of methylatedo-nitrophenol adduct of 4,4'-diglycidyloxy-α-methylstilbene from B aboveis dissolved in 1,4-dioxane (160 grams) and then added to a droppingfunnel. Sodium hydrosulfite (85% technical) (99.55 grams, 0.4860 moleactive), anhydrous potassium carbonate (67.17 grams, 0.4860 mole),deionized water (500 grams) and 1,4-dioxane (300 grams) are added to areactor and stirred to provide a solution. After cooling to 28° C., the1,4-dioxane solution of the nitro adduct is added dropwise to thereactor over a 65 minute period and so as to maintain the reactiontemperature at 28° C. The reaction product is maintained for anadditional seventeen hours while allowing the temperature to cool to 22°C. then stirring is shut off to allow separation of the aqueous andorganic layers to occur. The bottom aqueous layer is pipetted off anddiscarded, while the top organic layer is rotary evaporated to a drypowder using final conditions of 120° C. and 1 mm Hg. The dry powderproduct is added to 70° C. deionized water (400 milliliters) withstirring. Once a stirred solution is obtained it is allowed to cool to25° C., then isopropanol (2500 milliliters) is added in 300 milliliterportions to the stirred solution. After stirring the resulting slurryfor thirty minutes, then holding for 16 hours, filtration through amedium fritted glass funnel is completed and the product recovered onthe filter is washed with isopropanol (200 milliliters), then dried in avacuum oven at 80° C. and 1 mm Hg to a constant weight of 19.15 grams ofwhite powder. Fourier transform infrared spectrophotometric analysis ofa neat film of the product on a potassium chloride plate reveals thepresence of the expected primary amine group N--H stretching at 3436 and3389 cm⁻¹, concurrent with complete disappearance of the asymmetric andsymmetric nitro group stretching, and the methoxy group C--H stretchingat 2831 cm⁻¹. Titration of a portion of the product demonstrates thepresence of 3.2981 milequivalents of --NH₂ per gram of produce. Thisequates to a 303.21 --NH₂ equivalent weight, versus a 301.51 theoretical--NH₂ equivalent weight.

D. Analysis of the Methylated o-Aminophenol Adduct of4,4'-Diglycidyloxy-α-methylstilbene for Liquid Crystallinity

A portion (23.5 milligrams) of the adduct from C above is analyzed bydifferential scanning calorimetry using a heating rate of 10° C. perminute under a stream of nitrogen flowing at 35 cubic centimeters perminute and a temperature range from 30° to 300° C. An endotherm isobtained with an onset temperature of 84.5° C., a maximum at 103.4° C.,and an endpoint temperature 154.3° C. and an enthalpy of 5.50 joules pergram. A pair of exotherms follow with onset temperatures of 224.2 and251.4° C., maxima at 234.9 and 274.9° C., endpoint temperatures of251.4° and 291.9° C., and enthalpies of 22.2 and 18.7 joules per gram,respectively. Analysis of a portion of the methylated adduct viacrosspolarized light microscopy is completed using a microscope equippedwith a programmable hot stage using a heating rate of 10° C. per minuteand 70× magnification. The following results are obtained:

    ______________________________________                                        Observed                                                                      Transition                                                                    Temperatures (°C.)                                                                      Comments                                                     ______________________________________                                         25              Crystalline birefringent                                                      powder.                                                      145              First softening observed.                                    163              Birefringent fluid,                                                           suspended crystals observed.                                 205              Crystals dissolved, changes                                                   to fine grained uniform                                                       appearing birefringent                                                        fluid.                                                       225              Mobile birefringent fluid.                                   243              Viscosity builds,                                                             birefringent fluid.                                          265              Tacky solid, birefringent,                                                    darkens.                                                     ______________________________________                                    

When cooled to room temperature (24° C.), the product retains itsbirefringent appearance.

EXAMPLE 20 Copolymerization of Methylated o-Aminophenol Adduct of4,4'-Diglycidyoxy-α-methylstilbene with4,4'-Diglycidyloxy-α-methylstilbene Using 1:1 --NH to EpoxideStoichiometry

A portion (0.3326 gram, 0.002194>NH equivalent) of the methylatedo-aminophenol adduct of 4,4'-diglycidyloxy-α-methylstilbene from Example19-C and 4,4'-diglycidyloxy-α-methylstilbene (178,362 epoxide equivalentweight) (0.3913 gram, 0.002194 epoxide equivalent) are added to aceramic mortar and ground together until a homogeneous powder is formed.The 4,4'-diglycidyloxy-α-methylstilbene used has an epoxide equivalentweight (EEW) of 178.36 and exhibits monotropic liquid crystallinity witha 129.9° C. isotropization temperature, 92.9 onset to nematic liquidcrystallinity and a 67° C. onset to crystallization. A portion (19.0milligrams) of the adduct and epoxy resin blend is analyzed bydifferential scanning calorimetry using a heating rate of 10° C. perminute under a stream of nitrogen flowing at 35 cubic centimeters perminute and a temperature range from 30° to 300° C. An exotherm isobtained with an onset temperature of 61.3° C., a maximum at 78.5° C.,an endpoint temperature of 103.3° C. An endotherm is obtained with anonset temperature of 103.3° C., a minimum at 128.8° C., an endpointtemperature of 135.2° C. and an enthalpy of 34.7 joules per gram. A pairof exotherms follow with onset temperatures of 135.2° and 217.3° C.,maxima at 180.0 and 226.4° C., endpoint temperatures of 215.9° and239.9° C. followed by an exothermic rise and enthalpies of 56.6 and 24.1joules per gram, respectively. Analysis of the fused, light browncolored solid product recovered from the differential scanningcalorimetry analysis via crosspolarized light microscopy at 70×magnification revealed a high level of birefringence with nematictextures present.

What is claimed is:
 1. An adduct containing terminating nitro or nitrosogroups and one or more rodlike mesogenic moieties per molecule whichadduct results from the reaction of(A) one or more compounds containingan average of more than one vicinal epoxide group per molecule and (B)one or more compounds containing one or more nitro or nitroso groups andone hydrogen atom per molecule which is reactive with an epoxide groupthereby forming an adduct essentially free of epoxy groups andcontaining nitro groups;with the proviso that said at least one or morerodlike mesogenic moieties per molecule are present in either component(A) or (B) or in both components (A) and (B), wherein components (A) and(B) are employed in amounts which provide a ratio of equivalents ofhydrogen reactive with an epoxide group, excluding secondary hydroxylgroups formed by epoxide ring opening reaction to form the adduct, perequivalent of epoxide reacted of from about 1:1 to about 100:1.
 2. Anitro or nitroso group terminated adduct of claim 1 wherein component(A) contains a compound containing one or more rodlike mesogenicmoieties per molecule.
 3. A nitro or nitroso group terminated adduct ofclaim 2 wherein component (A) is a compound represented by the followingFormulas II, V, VI or IX ##STR15## wherein each A is independentlyselected from the group consisting of a direct single bond, --CR¹ ═CR¹--, --C.tbd.C--, --N═N--, --CR¹ ═N--, --O--CO--, --NR¹ --CO--, --CR¹═N--N═CR¹ --, --CR¹ ═CR¹ --CO--, --N═CR¹ --, --CO--O--, --CO--NR¹ --,--CO--CR¹ ═CR¹ --, --CO--O--N═CR¹, --CR¹ ═N--O--OC--, --CO--NR¹ --NR¹--OC--, --CR¹ ═CR¹ --O--OC--, --CO--O--CR¹ ═CR¹ --, --O--OC--CR¹ ═CR¹--, --CR¹ ═CR¹ --CO--O--, --(CHR¹)_(n') --O--CO--CR¹ ═CR¹ --, --CR¹ ═CR¹--CO--O--(CHR¹)_(n') --, --(CHR¹)_(n') --CO--O--CR.sup. 1 ═CR¹ --, --CR¹═CR¹ --O--CO--(CHR¹)_(n') --, --CO--S--, --S--OC--, --CH₂ --CH₂--CO--O--, --O--OC--CH₂ --CH₂ --, --C.tbd.C--C.tbd.C--, --CR¹ ═CR¹ --CR¹═CR¹ --, ##STR16## A' is a divalent hydrocarbyl group having from 1 toabout 10 carbon atoms and in Formula VI, A' can also contain one or moreheteroatoms selected from N, O and S and may be saturated orunsaturated; each A¹ is independently a ##STR17## each R isindependently hydrogen or a hydrocarbyl or hydrocarbyloxy group havingfrom 1 to about 10 carbon atoms, a halogen atom, a nitro group, anitrile group, a phenyl group or a --CO--R¹ group; each R¹ isindependently hydrogen or a hydrocarbyl group having 1 to about 3 carbonatoms; n is zero or 1; n' has a value from 1 to about 6; z has a valueof one or two; p has a value from zero to about 30; p¹ has a value from1 to about 30; and the aromatic rings can optionally contain one or moreheteroatoms selected from the group consisting of N, O and S; with theproviso that at least 80% of the molecules are para substituted by thebridging groups (--A-- in Formulas II, V IX and by the direct bond inFormula VI), the substituent containing the glycidyl group(s), ##STR18##and the substituent containing the secondary hydroxy alkylidenegroup(s), --CH₂ --C(OH)(R¹)--CH₂ --, which are present when p or p¹ hasa value greater than zero.
 4. A nitro or nitroso group terminated adductof claim 2 wherein component (A) is the diglycidyl ether of4,4'-dihydroxy-α-methylstilbene, 4,4'-dihydroxystilbene,4,4'-dihydroxybenzanilide, 4,4'-dihydroxybiphenyl,4-hydroxyphenyl-4-hydroxybenzoate,N,N'-bis(4-hydroxyphenyl)terephthalamide,bis(4-hydroxyphenyl)terephthalate, or any combination thereof.
 5. Anitro or nitroso group terminated adduct of claim 1 wherein component(B) contains a compound containing one or more mesogenic moieties permolecule.
 6. A nitro or nitroso group terminated adduct of claim 5wherein component (B) is selected from the group consisting of: (a)nitro and nitrosophenols, (b) nitro and nitrosocarboxylic acids, (c)nitro and nitrosomercaptans, (d) nitro and nitroso secondary monoamines,and (e) any combination of any two or more of such materials.
 7. A nitroor nitroso group terminated adduct of claim 5 wherein component (B) is anitro or nitrosophenol represented by the Formulas XXI, XXIII or XXIV##STR19## wherein each A is independently selected from the groupconsisting of a direct single bond, --CR¹ ═CR¹ --, --C.tbd.C--, --N═N--,--CR¹ ═N--, --O--CO--, --NR¹ --CO--, --CR¹ ═N--N═CR¹ --, --CR¹ ═CR¹--CO--, --N═CR¹ --, --CO--O--, --CO--NR¹ --, --CO--CR¹ ═CR¹ --,--CO--O--N═CR¹, --CR¹ ═N--O--OC--, --CO--NR¹ --NR¹ --OC--, --CR¹ ═CR¹--O--OC--, --CO--O--CR¹ ═CR¹ --, --O--OC--CR¹ ═CR¹ --, --CR¹ ═CR¹--CO--O--, --(CHR¹)_(n') --O--CO--CR¹ ═CR¹ --, --CR¹ ═CR¹--CO--O--(CHR¹)_(n') --, --(CHR¹)_(n') --CO--O--CR¹ ═CR¹ --, --CR¹ ═CR¹--O--CO--(CHR¹)_(n') --, --CO--S--, --S--OC--, --CH₂ --CH₂ --CO--O--,--O--OC--CH₂ --CH₂ --, --C.tbd.C--C.tbd.C--, --CR¹ ═CR¹ --CR¹ ═CR¹ --,##STR20## A' is a divalent hydrocarbyl group having from 1 to about 10carbon atoms and A' in Formula XXIV can also contain one or moreheteroatoms selected from N, O and S and may be saturated orunsaturated; each A¹ is independently a ##STR21## one Y is a --OH groupand the other Y becomes a R group and one or more of the groupsrepresented by R is a nitro or nitroso group; each R is independentlyhydrogen or a hydrocarbyl or hydrocarbyloxy group having from 1 to about10 carbon atoms, a halogen atom, a nitro group, a nitroso group, anitrile group, a phenyl group or a --CO--R¹ group; each R¹ isindependently hydrogen or a hydrocarbyl group having 1 to about 3 carbonatoms; n is zero or 1; n' has a value from 1 to about 6; z has a valueof one or two; p¹ has a value from 1 to about 30; and the aromatic ringscan optionally contain one or more heteroatoms selected from the groupconsisting of N, O and S; with the proviso that at least about 80% ofthe molecules are para substituted by both the bridging groups (--A-- inFormulas XXI and XXIII, the direct bond in Formula XXIV) and thehydroxyl group (--OH).
 8. A nitro or nitroso group terminated adduct ofclaim 7 wherein component (B) is 4-hydroxy-4'-nitrobiphenyl,4-hydroxy-4'-nitrostilbene, 4-hydroxy-4'-nitrodiphenylazomethine,4-hydoxy-4'-nitroazoxybenzene, 4-hydroxy-4'-nitrobenzanilide,4-nitro-4'-hydroxybenzanilide, 4-hydroxyphenyl-4'-nitrobenzoate,4-hydroxy-4'-nitro-alpha-chlorostilbene, or any combination thereof. 9.A nitro or nitroso group terminated adduct of claim 5 wherein component(B) is a nitro or nitrosocarboxylic acid represented by the followingFormulas XXI, XXIV or XXV ##STR22## wherein each A is independentlyselected from the group consisting of a direct single bond, --CR¹ ═CR¹--, --C.tbd.--, --N═N--, --CR¹ ═N--, --O--CO--, --NR¹ --CO--, --CR¹═N--N═CR¹ --, --CR¹ ═CR¹ --CO--, --N═CR¹ --, --CO--O--, --CO--NR¹ --,--CO--CR¹ ═CR¹ --, --CO--O--N═CR¹, --CR¹ ═N--O--OC--, --CO--NR¹ --NR¹--OC--, --CR¹ ═CR¹ --O--OC--, --CO--O--CR¹ ═CR¹ --, --O--OC--CR¹ ═CR¹--, --CR¹ ═CR¹ --CO--O--, --(CHR¹)_(n') --O--CO--CR¹ ═CR¹ --, --CR¹ ═CR¹--CO--O--(CHR¹)_(n') --, --(CHR¹)_(n') --CO--O--CR¹ ═CR¹ --, --CR¹ ═CR¹--O--CO--(CHR¹)_(n') --, --CO--S--, --S--OC--, --CH₂ --CH₂ --CO--O--,--O--OC--CH₂ --CH₂ --, --C.tbd.C--C.tbd.C--, --CR¹ ═CR¹ --CR¹ ═CR¹ --,##STR23## A' is a divalent hydrocarbyl group having from 1 to about 10carbon atoms and A' in Formula XXIV can also contain one or moreheteroatoms selected from N, O and S and may be saturated orunsaturated; each A¹ is independently a ##STR24## one Y is a --COOHgroup and the other Y becomes a R group and one or more of the groupsrepresented by R is a nitro or nitroso group; each R is independentlyhydrogen or a hydrocarbyl or hydrocarbyloxy group having from 1 to about10 carbon atoms, a halogen atom, a nitro group, a nitroso group, anitrile group, a phenyl group or a --CO--R¹ group; each R¹ isindependently hydrogen or a hydrocarbyl group having 1 to about 3 carbonatoms; n is zero or 1; n' has a value from 1 to about 6; z has a valueof one or two; p¹ has a value from 1 to about 30; and the aromatic ringscan optionally contain one or more heteroatoms selected from the groupconsisting of N, O and S; with the proviso that at least 80% of themolecules are para substituted by the bridging groups (--A-- in FormulasXXI and XXIII, the direct bond in Formula XXIV) and the carboxyl group(--COOH).
 10. A nitro or nitroso group terminated adduct of claim 9wherein component (B) is 4-carboxy-4'-nitrobiphenyl,4-carboxy-4'-nitrostilbene, 4-carboxy-4'-nitrodiphenylazomethine,4-carboxy-4'-nitroazoxybenzene, 4-carboxy-4'-nitrobenzanilide,4-nitro-4'-carboxybenzanilide, 4-carboxyphenyl-4'-nitrobenzoate,4-carboxy-4'-nitro-alpha-chlorostilbene, or any combination thereof. 11.A nitro or nitroso group terminated adduct of claim 5 wherein component(B) is a nitro or nitrosomercaptan represented by the following FormulasXXI, XXIII or XXIV ##STR25## wherein each A is independently selectedfrom the group consisting of a direct single bond, --CR¹ ═CR¹ --,--C.tbd.C--, --N═N--, --CR¹ ═N--, --O--CO--, --NR¹ --CO--, --CR¹═N--N═CR¹ --, --CR¹ ═CR¹ --CO--, --N═CR¹ --, --CO--O--, --CO--NR¹ --,--CO--CR¹ ═CR¹ --, --CO--O--N═CR¹, --CR¹ ═N--O--OC--, --CO--NR¹ --NR¹--OC--, --CR¹ ═CR¹ --O--OC--, --CO--O--CR¹ ═CR¹ --, --O--OC--CR¹ ═CR¹--, --CR¹ ═CR¹ --CO--O--, --(CHR¹)_(n') --O--CO--CR¹ ═CR¹ --, --CR¹ ═CR¹--CO--O--(CHR¹)_(n') --, --(CHR¹)_(n') --CO--O--CR.sup. 1 ═CR¹ --, --CR¹═CR¹ --O--CO--(CHR¹)_(n') --, --CO--S--, --S--OC--, --CH₂ --CH₂--CO--O--, --O--OC--CH₂ --CH₂ --, --C.tbd.C--C.tbd.C--, --CR¹ ═CR¹ --CR¹═CR¹ --, ##STR26## A' is a divalent hydrocarbyl group having from 1 toabout 10 carbon atoms and A' in Formula XXIV can also contain one ormore heteroatoms selected from N, O and S and may be saturated orunsaturated; each A¹ is independently a ##STR27## each R isindependently hydrogen or a hydrocarbyl or hydrocarbyloxy group havingfrom 1 to about 10 carbon atoms, a halogen atom, a nitro group, anitroso group, a nitrile group, a phenyl group or a --CO--R¹ group; eachR¹ is independently hydrogen or a hydrocarbyl group having 1 to about 3carbon atoms; one Y is a --SH group and the other Y becomes a R groupand one or more of the groups represented by R is a nitro or nitrosogroup; n is zero or 1; n' has a value from 1 to about 6; z has a valueof one or two; p¹ has a value from 1 to about 30; and the aromatic ringscan optionally contain one or more heteroatoms selected from the groupconsisting of N, O and S; with the proviso that at least 80% of themolecules are para substituted by the bridging groups (--A-- in FormulasXXI and XXII, the direct bond in Formula XXIV and the mercaptan group(--SH).
 12. A nitro or nitroso group terminated adduct of claim 11wherein component (B) is 4-mercapto-4'-nitrobiphenyl,4-mercapto-4'-nitrostilbene, 4-mercapto-4'-nitrodiphenylazomethine,4-mercapto-4'-nitroazoxybenzene, 4-mercapto-4'-nitrobenzanilide,4-nitro-4'-mercaptobenzanilide, 4-mercaptophenyl-4'-nitrobenzoate,4-mercapto-4'-nitro-alpha-chlorostilbene, or any combination thereof.13. A nitro or nitroso group terminated adduct of claim 5 whereincomponent (B) is a nitro or nitroso secondary monoamine represented bythe following Formulas XXI, XXIII or XXIV ##STR28## wherein each A isindependently selected from the group consisting of a direct singlebond, --CR¹ ═CR¹ --, --C.tbd.C--, --N═N--, --CR¹ ═N--, --O--CO--, --NR¹--CO--, --CR¹ ═N--N═CR¹ --, --CR¹ ═CR¹ --CO--, --N═CR¹ --, --CO--O--,--CO--NR¹ --, --CO--CR¹ ═CR¹ --, --CO--O--N═CR¹, --CR¹ ═N--O--OC--,--CO--NR¹ --NR¹ --OC--, --CR¹ ═CR¹ --O--OC--, --CO--O--CR¹ ═CR¹ --,--O--OC--CR¹ ═CR¹ --, --CR¹ ═CR¹ --CO--O--, --(CHR¹)_(n') --O--CO--CR¹═CR¹ --, --CR¹ ═CR¹ --CO--O--(CHR¹)_(n') --, --(CHR¹)_(n') --CO--O--CR¹CR¹ --, --CR¹ ═CR¹ --O--CO--(CHR¹)_(n') --, --CO--S--, --S--OC--, --CH₂--CH₂ --CO--O--, --O--OC--CH₂ --CH₂ --, --C.tbd.C--C.tbd.C--, --CR¹ ═CR¹--CR¹ ═CR¹ --, ##STR29## A' is a divalent hydrocarbyl group having from1 to about 10 carbon atoms and A' in Formula XXIV can also contain oneor more heteroatoms selected from N, O and S any may be saturated orunsaturated; each A¹ is independently a ##STR30## one Y is a --NHR⁴group and the other Y becomes a R group and one or more of the groupsrepresented by R is a nitro or nitroso group; R⁴ is a hydrocarbyl grouphaving from 1 to about 12 carbon atoms; each R is independently hydrogenor a hydrocarbyl or hydrocarbyloxy group having from 1 to about 10carbon atoms, a halogen atom, a nitro group, a nitroso group, a nitrilegroup, a phenyl group or a --CO--R¹ group; each R1 is independentlyhydrogen or a hydrocarbyl group having 1 to about 3 carbon atoms; n iszero or 1; n' has a value from 1 to about 6; z has a value of one ortwo; p¹ has a value from 1 to about 30; and the aromatic rings canoptionally contain one or more heteroatoms selected from the groupconsisting of N, O and S; with the proviso that at least 80% of themolecules are para substituted by both the bridging groups (--A-- inFormulas XXI and XXIII, the direct bond in Formula XXIV) and the aminogroups (--NHR⁴).
 14. A nitro or nitroso group terminated adduct of claim13 wherein component (B) is 4-N-methylamino-4'-nitrobiphenyl,4-N-methylamino-4'-nitrostilbene,4-N-methylamino-4'-nitrodiphenylazomethine,4-N-methylamino-4'-nitroazoxybenzene,4-N-methylamino-4'-nitrobenzanilide,4-nitro-4'-N-methylaminobenzanilide,4-N-methylaminophenyl-4'-nitrobenzoate,4-N-methylamino-4'-nitro-alpha-chlorostilbene, or any combinationthereof.
 15. A nitro or nitroso group terminated adduct of claim 1wherein both of the components (A) and (B) contain a compound which hasat least one rodlike mesogenic moiety per molecule.
 16. A nitro ornitroso group terminated adduct of claim 15 wherein(a) component (A) isan epoxy resin containing at least one rodlike mesogenic moiety selectedfrom the same group as those in claim 3; and (b) component (B) is asingle active hydrogen containing compound containing one or more nitro(nitroso) groups and at least one rodlike mesogenic moiety selected fromthe same group as those in claim
 6. 17. An adduct of claim 16 wherein(a)component (A) is selected from the group consisting of the diglycidylethers of: 4,4'-dihydroxy-α-methylstilbene, 4,4'-dihydroxystilbene,4,4'-dihydroxybenzanilide, 4,4'-dihydroxybiphenyl,4-hydroxyphenyl-4-hydroxybenzoate,N,N'-bis(4-hydroxyphenyl)terephthalamide,bis(4-hydroxyphenyl)terephthalate, and any combination thereof; and (b)component (B) is selected from the group consisting of 4-hydroxy-4'-nitrobiphenyl, 4-hydroxy-4'-nitrostilbene,4-hydroxy-4'-nitrodiphenylazomethine, 4-hydoxy-4'-nitroazoxybenzene,4-hydroxy-4'-nitrobenzanilide, 4-nitro-4'-hydroxybenzanilide,4-hydroxyphenyl-4'-nitrobenzoate,4-hydroxy-4'-nitro-alpha-chlorostilbene, 4-carboxy-4'-nitrobiphenyl,4-carboxy-4'-nitrostilbene, 4-carboxy-4'-nitrodiphenylazomethine,4-carboxy-4'-nitroazoxybenzene, 4-carboxy-4'-nitrobenzanilide,4-nitro-4'-carboxybenzanilide, 4-carboxyphenyl-4'-nitrobenzoate,4-carboxy-4'-nitro-alpha-chlorostilbene, 4-mercapto-4'-nitrobiphenyl,4-mercapto-4'-nitrostilbene, 4-mercapto-4'-nitrodiphenylazomethine,4-mercapto-4'-nitroazoxybenzene, 4-mercapto-4'-nitrobenzanilide,4-nitro-4'-mercaptobenzanilide, 4-mercaptophenyl-4'-nitrobenzoate,4-mercapto-4'-nitro-alpha-chlorostilbene,4-N-methylamino-4'-nitrobiphenyl, 4-N-methylamino-4'-nitrostilbene,4-N-methylamino-4'-nitrodiphenylazomethine,4-N-methylamino-4'-nitroazoxybenzene,4-N-methylamino-4'-nitrobenzanilide,4-nitro-4'-N-methylaminobenzanilide,4-N-emthylaminophenyl-4'-nitrobenzoate,4-N-methylamino-4'-nitro-alpha-chlorostilbene, or any combinationthereof.